Multiphase coatings with separated functional particles, and methods of making and using the same

ABSTRACT

Some variations provide a multiphase polymer composition comprising a first polymer material and a second polymer material that are chemically distinct, wherein the first polymer material and the second polymer material are microphase-separated on a microphase-separation length scale from about 0.1 microns to about 500 microns, wherein the multiphase polymer composition comprises first solid functional particles selectively dispersed within the first polymer material, and wherein the first solid functional particles are chemically distinct from the first polymer material and the second polymer material. Some embodiments provide an anti-corrosion composition comprising first corrosion-inhibitor particles or precursors selectively dispersed within the first polymer material, wherein the multiphase polymer composition optionally further comprises second corrosion-inhibitor particles or precursors selectively dispersed within the second polymer material. These multiphase polymer compositions may be used for other applications, such as self-cleaning, self-healing, or flame-retardant coatings. Methods of making and using these multiphase polymer compositions are disclosed.

PRIORITY DATA

This patent application is a continuation application of U.S. Pat. No.11,225,589, issued on Jan. 18, 2022, which is a divisional of U.S. Pat.No. 10,689,542, issued on Jun. 23, 2020, which in turn claims priorityto (a) U.S. Provisional Patent App. No. 62/543,590, filed on Aug. 10,2017; (b) U.S. Provisional Patent App. No. 62/607,402, filed on Dec. 19,2017; and (c) U.S. Provisional Patent App. No. 62/634,990, filed on Feb.26, 2018, each of which is hereby incorporated by reference herein.

FIELD OF THE INVENTION

The present invention generally relates to multiphase coatings andmethods of making multiphase coatings.

BACKGROUND OF THE INVENTION

A coating is a covering that is applied to the surface of an object,usually referred to as the substrate. The purpose of applying thecoating may be decorative, functional, or both. Practically everymanufactured product requires a coating, often for protective purposes.A major use of coatings is to prevent or counteract the effects ofcorrosion.

Corrosion is a naturally occurring process that causes significantchanges to the physical structure of a material, usually a metal. Thesechanges can be caused by a chemical reaction when metals are exposed towater, acids, or gases. Corrosion weakens the physical structure of thematerial and can eventually lead to failure of the affected component.By the time corrosion is visible, the damage can be very costly torepair. National Association of Corrosion Engineers (NACE) estimatesthat the direct costs for preventing, mitigating, and repairingcorrosion in the United States are $276 billion annually, and indirectcosts such as lost productivity, litigation, and environmentalmitigation may push the total corrosion bill to more than $550 billion(Lalgudi et al., “The Science of Corrosion-Busting Smart Coatings”,Paint & Coatings Industry, Mar. 1, 2016).

Generally, various particles can be introduced into coatings. However,commercial coatings include only one reactive particle, or multipleunreactive particles, because of processing limitations. There are noknown methods to keep reactive species from interacting during thesynthesis. Many coatings are synthesized in a single reaction vesselwith sequential additions of the various components. Even if theresulting coating displays a desired phase-separated morphology, thecomponents themselves are in contact prior to phase separation. Thiscommon procedure does not allow for two different reactive particles tobe segregated into a certain phase.

There is a need for a new capability to fabricate multifunctionalcoatings with reactive particles that cannot normally be mixed orassociated with one another. In view of the shortcomings in the art,improved coating materials and systems, and compositions suitable forthese systems, are needed, especially to maintain the mechanicalintegrity of the coating for corrosion resistance and otherapplications. In particular, what is desired commercially is an entirelynew platform, enabling the fabrication of coatings and materials withmultiple functional additives, in an industrially scalable process.

SUMMARY OF THE INVENTION

The present invention addresses the aforementioned needs in the art, aswill now be summarized and then further described in detail below.

Some variations provide a multiphase polymer composition comprising afirst polymer material and a second polymer material that are chemicallydistinct, wherein the first polymer material and the second polymermaterial are microphase-separated on a microphase-separation lengthscale from about 0.1 microns to about 500 microns, wherein themultiphase polymer composition comprises first solid functionalparticles selectively dispersed within the first polymer material, andwherein the first solid functional particles are chemically distinctfrom the first polymer material and the second polymer material.

In some embodiments, the first solid functional particles are capable ofreacting with the second polymer material, in response to anenvironmental input selected from the group consisting of ultravioletlight, change in temperature, change in pressure, environmentalsolvents, change in humidity, change in pH, and combinations thereof.

In some embodiments, the multiphase polymer composition is disposed on asurface, and the first solid functional particles are capable ofreacting with the surface, in response to an environmental inputselected from the group consisting of ultraviolet light, change intemperature, change in pressure, environmental solvents, change inhumidity, change in pH, and combinations thereof.

The first solid functional particles may be dissolvable in water or anaqueous solvent. Alternatively, or additionally, the first solidfunctional particles may be dissolvable in an organic solvent. Any ofthese solvents may be environmental solvents, i.e. fluids derived fromthe local environment, such as rain, ocean spray, melted snow or ice,humidity, fuel, cleaning fluid, hydraulic fluid, or anti-icing fluid.

In some variations, the multiphase polymer composition further comprisessecond solid functional particles selectively dispersed within thesecond polymer material, wherein the second solid functional particlesare chemically distinct from the first polymer material and the secondpolymer material. In certain embodiments, the second solid functionalparticles are essentially not contained at all within the first polymermaterial.

When second solid functional particles are present, the first solidfunctional particles and the second solid functional particles may becapable of reacting with each other in response to an environmentalinput selected from the group consisting of ultraviolet light, change intemperature, change in pressure, environmental solvents, change inhumidity, change in pH, and combinations thereof.

When second solid functional particles are present, they may be capableof reacting with the first polymer material, in response to anenvironmental input selected from the group consisting of ultravioletlight, change in temperature, change in pressure, environmentalsolvents, change in humidity, change in pH, and combinations thereof.

In some embodiments, the multiphase polymer composition is disposed on asurface, and the second solid functional particles are included andcapable of reacting with the surface, in response to an environmentalinput selected from the group consisting of ultraviolet light, change intemperature, change in pressure, environmental solvents, change inhumidity, change in pH, and combinations thereof.

The second solid functional particles may be dissolvable in water or anaqueous solvent. Alternatively, or additionally, the second solidfunctional particles may be dissolvable in an organic solvent. Any ofthese solvents may be environmental solvents, i.e. fluids derived fromthe local environment, such as rain, ocean spray, melted snow or ice,humidity, fuel, cleaning fluid, hydraulic fluid, or anti-icing fluid.

The first solid functional particles may include inorganic particles,organic particles, or a combination thereof. The second solid functionalparticles, when present, may include inorganic particles, organicparticles, or a combination thereof.

The first solid functional particles may include oxidizing agents,reducing agents, or a combination thereof. The second solid functionalparticles, when present, may include oxidizing agents, reducing agents,or a combination thereof.

The first solid functional particles may be selected from the groupconsisting of metals, metal oxides, organic oxides, ceramics, salts,polymers, and combinations thereof. The second solid functionalparticles, when present, may be selected from the group consisting ofmetals, metal oxides, organic oxides, ceramics, salts, polymers, andcombinations thereof.

The first solid functional particles may be surface-treated to enhancechemical compatibility with the first polymer material. The second solidfunctional particles, when present, may be surface-treated to enhancechemical compatibility with the second polymer material. Surfacetreatment may adjust properties such as hydrophobicity, hydrophilicity,surface tension, polarity, and solubility.

The first solid functional particles may have an average particle sizefrom about 50 nanometers to about 500 microns, for example. The secondsolid functional particles, when present, may have an average particlesize from about 50 nanometers to about 500 microns, for example.

In various embodiments, the first polymer material and the secondpolymer material are independently selected from the group consisting ofpolyesters, polyethers, polyacrylates, polymethacrylates, polyepoxides,polysiloxanes, cellulosic polymers, and combinations thereof.

Polyesters and polyethers may be selected from the group consisting ofperfluoropolyethers, polyfluoroacrylates, polyfluorosiloxanes,polyvinylidene fluoride, polytrifluoroethylene, poly(oxymethylene),poly(ethylene glycol), poly(propylene oxide), poly(tetrahydrofuran),poly(glycolic acid), poly(caprolactone), poly(ethylene adipate),poly(hydroxyl butyrate), poly(hydroxyl alkanoate), and combinationsthereof.

Polyacrylates, polymethacrylates, polyepoxides, polysiloxanes, andcellulosic polymers may be selected from the group consisting ofpolymethylmethacrylate, poly(acrylic acid), poly(2-hydroxyethylmethacrylate), poly(vinyl imidazole), poly(2-methyl-2-oxazoline),poly(2-ethyl-2-oxazoline), poly(vinylpyrolidone), polydimethylsiloxane,cellulose, cellulose hydrogels, methyl cellulose, carboxymethylcellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, andcombinations thereof.

In some embodiments, one of the first polymer material or the secondpolymer material is a continuous matrix, and the other of the firstpolymer material or the second polymer material is a plurality ofinclusions, dispersed within the continuous matrix. Either thecontinuous matrix or the inclusions may be the first polymer materialcontaining the first solid functional particles, and the continuousmatrix or inclusions that do not contain the first solid functionalparticles optionally contain second solid functional particles.

The continuous matrix and the inclusions may be covalently bonded witheach other, directly or via reactive species contained within and/orbetween the continuous matrix and the inclusions. In some embodiments,the reactive species include an isocyanate species and an alcohol oramine with functionality of 2 or greater. An isocyanate species may beselected from the group consisting of 4,4′-methylenebis(cyclohexylisocyanate), hexamethylene diisocyanate, cycloalkyl-based diisocyanates,tolylene-2,4-diisocyanate, 4,4′-methylenebis(phenyl isocyanate),isophorone diisocyanate, and combinations or derivatives thereof. Inthese or other embodiments, the reactive species includes an epoxy andan alcohol, amine, or thiol with functionality of 2 or greater.

In some embodiments, the continuous matrix and the inclusions arecovalently bonded with each other via reactive species, in a segmentedblock copolymer containing first soft segments and second soft segments,wherein one of the continuous matrix or the inclusions contain the firstsoft segments, and wherein the other of the continuous matrix or theinclusions contain the second soft segments.

Generally, the multiphase polymer composition contains a segmented blockcopolymer, wherein the first polymer material contains or consistsessentially of first soft segments of the segmented block copolymer, andwherein the second polymer material contains or consists essentially ofsecond soft segments of the segmented block copolymer.

In certain embodiments, the segmented copolymer composition comprises:

(a) one or more the first soft segments selected from fluoropolymershaving an average molecular weight from about 500 g/mol to about 10,000g/mol, wherein the fluoropolymers are (α,ω)-hydroxyl-terminated and/or(α,ω)-amine-terminated;

(b) one or more the second soft segments selected from polyesters orpolyethers, wherein the polyesters or polyethers are(α,ω)-hydroxyl-terminated and/or (α,ω)-amine-terminated, wherein themolar ratio of the second soft segments to the first soft segments isoptionally less than 2.0;

(c) one or more isocyanate species, or a reacted form thereof,possessing an isocyanate functionality of 2 or greater; and

(d) one or more polyol or polyamine chain extenders or crosslinkers, ora reacted form thereof.

The fluoropolymer may be selected from the group consisting ofpolyfluoroethers, perfluoropolyethers, polyfluoroacrylates,polyfluorosiloxanes, polytetrafluoroethylene, polyvinylidene difluoride,polyvinylfluoride, polychlorotrifluoroethylene, copolymers of ethyleneand trifluoroethylene, copolymers of ethylene andchlorotrifluoroethylene, and combinations thereof.

The fluoropolymers may be present in the triblock structure:

wherein:X, Y═CH₂—(O—CH₂—CH₂)_(p)-T, and X and Y are independently selected;p=1 to 50;T is a hydroxyl or amine terminal group;m=1 to 100; andn=0 to 100.

The isocyanate species may be selected from the group consisting of4,4′-methylenebis(cyclohexyl isocyanate), hexamethylene diisocyanate,cycloalkyl-based diisocyanates, tolylene-2,4-diisocyanate,4,4′-methylenebis(phenyl isocyanate), isophorone diisocyanate, andcombinations or derivatives thereof.

The polyol or polyamine chain extenders or crosslinkers may be selectedfrom the group consisting of 1,3-butanediol, 1,4-butanediol,1,3-propanediol, 1,2-ethanediol, diethylene glycol, triethylene glycol,tetraethylene glycol, propylene glycol, dipropylene glycol, tripropyleneglycol, neopentyl glycol, 1,6-hexanediol, 1,4-cyclohexanedimethanol,ethanol amine, diethanol amine, methyldiethanolamine,phenyldiethanolamine, glycerol, trimethylolpropane, 1,2,6-hexanetriol,triethanolamine, pentaerythritol, ethylenediamine, 1,3-propanediamine,1,4-butanediamine, diethyltoluenediamine, dimethylthiotoluenediamine,isophoronediamine, diaminocyclohexane,N,N,N′,N′-tetrakis(2-hydroxypropyl) ethylenediamine, and homologues,derivatives, or combinations thereof. In certain embodiments, the polyolor polyamine chain extenders or crosslinkers possess an averagefunctionality of about 3 or greater.

Optionally, the multiphase polymer composition may further include oneor more additional components selected from the group consisting of aparticulate filler, a pigment, a dye, a plasticizer, a flame retardant,and combinations thereof. The particulate filler may be selected fromthe group consisting of silica, alumina, silicates, talc,aluminosilicates, barium sulfate, mica, diatomite, calcium carbonate,calcium sulfate, carbon, wollastonite, and combinations thereof.

The multiphase polymer composition may be present in or as a coating,such as (but not limited to) an anti-corrosion coating applied to ametallic substrate.

Some variations of the invention provide an anti-corrosion compositioncomprising a first polymer material and a second polymer material thatare chemically distinct, wherein the first polymer material and thesecond polymer material are microphase-separated on amicrophase-separation length scale from about 0.1 microns to about 500microns, wherein the multiphase polymer composition comprises firstcorrosion-inhibitor particles or precursors selectively dispersed withinthe first polymer material, wherein the multiphase polymer compositionoptionally further comprises second corrosion-inhibitor particles orprecursors selectively dispersed within the second polymer material, andwherein the first corrosion-inhibitor particles or precursors and thesecond corrosion-inhibitor particles or precursors are chemicallydistinct from the first polymer material and the second polymermaterial.

In some embodiments, the first corrosion-inhibitor particles orprecursors and/or the second corrosion-inhibitor particles or precursors(when present) are selected from the group consisting of redoxreaction-type inhibitors, hydrolysis reaction-type inhibitors, anodicpolarization-type inhibitors, adsorbate-type inhibitors, andcombinations thereof.

In some embodiments employing the second corrosion-inhibitor particlesor precursors, the first corrosion-inhibitor particles or precursors andthe second corrosion-inhibitor particles or precursors are capable ofreacting with each other in response to an environmental input selectedfrom the group consisting of ultraviolet light, change in temperature,change in pressure, environmental solvents, change in humidity, changein pH, and combinations thereof.

In some embodiments employing the second corrosion-inhibitor particlesor precursors, the anti-corrosion composition is disposed on ametal-containing substrate, wherein the first corrosion-inhibitorparticles or precursors and the second corrosion-inhibitor particles orprecursors are capable of reacting with each other to form a passivationcoating or anti-corrosion layer on the metal-containing substrate. Ananti-corrosion layer reduces the corrosion potential of the underlyingmetal-containing substrate.

In certain exemplary embodiments, the first corrosion-inhibitorparticles or precursors include ammonium hexafluorotitanate and/orchromium(III) oxide, and the second corrosion-inhibitor particles orprecursors include boric acid and/or potassium permanganate.

Variations of the invention also provide a method of making a multiphasepolymer composition, the method comprising:

(a) in a first reaction container, synthesizing a first polymer materialfrom first-polymer starting components;

(b) in a second reaction container, synthesizing a second polymermaterial from second-polymer starting components, wherein the secondpolymer material is chemically distinct from the first polymer material;

(c) introducing a plurality of first solid functional particles into thefirst reaction container, to dispose the first solid functionalparticles in the first polymer material, wherein the first solidfunctional particles are chemically distinct from the first polymermaterial and the second polymer material;

(d) optionally introducing a plurality of second solid functionalparticles into the second reaction container, to disperse the secondsolid functional particles in the second polymer material;

(e) providing reactive species capable of covalently bonding the firstpolymer material with the second polymer material; and

(f) combining the first polymer material, the second polymer material,and the reactive species to covalently bond the first polymer materialwith the second polymer material, thereby generating a multiphasepolymer composition,

wherein the multiphase polymer composition comprises the first solidfunctional particles selectively dispersed within the first polymermaterial, and wherein the first polymer material and the second polymermaterial are microphase-separated on a microphase-separation lengthscale from about 0.1 microns to about 500 microns.

When (d) is performed, the multiphase polymer composition comprises thesecond solid functional particles selectively dispersed within thesecond polymer material.

The multiphase polymer composition may be present in or as a coating. Insome method embodiments, the first solid functional particles react inresponse to damage to the coating. The reaction can be with other firstsolid functional particles, with the second solid functional particles(when present), with a surface, with a fluid, or any combinationthereof.

In some method embodiments, the first solid functional particles reactupon exposure to ultraviolet light, a change in temperature, a change inpH, a change in pressure, or a combination thereof. In some embodiments,the second solid functional particles also react upon exposure toultraviolet light, a change in temperature, a change in pH, a change inpressure, or a combination thereof.

The first solid functional particles, the second solid functionalparticles, or both of these may be dissolved in aqueous or organicsolvent that originates from the environment. For example, an aqueous ororganic solvent may be selected from the group consisting of atmospherichumidity, rain, ocean spray, melted snow or ice, fuel, cleaning fluid,hydraulic fluid, anti-icing fluid, and combinations thereof.

In some methods, the coating is an anti-corrosion coating applied to ametallic substrate, wherein the first solid functional particles includefirst corrosion-inhibitor particles or precursors. The first solidfunctional particles may react with the metallic substrate to form apassivation coating or an anti-corrosion layer. The first solidfunctional particles may react with an aqueous or organic fluid thatoriginates from the environment, such as atmospheric humidity, rain,ocean spray, fuel, cleaning fluid, hydraulic fluid, or anti-icing fluid,for example.

In some methods in which step (d) is performed and when the multiphasepolymer composition is present in or as an anti-corrosion coatingapplied to a metallic substrate, the second solid functional particlesinclude second corrosion-inhibitor particles or precursors. In theseembodiments, the first solid functional particles and the second solidfunctional particles may react with each other to form a passivationcoating or an anti-corrosion layer. In some embodiments, the first solidfunctional particles and the second solid functional particles reactwith each other and the metallic substrate to form a passivation coatingor an anti-corrosion layer. In certain embodiments, the first solidfunctional particles and the second solid functional particles reactwith each other, the metallic substrate, and an aqueous or organic fluidthat originates from the environment, to form a passivation coating oran anti-corrosion layer.

BRIEF DESCRIPTION OF THE DRAWINGS

The patent or application file contains at least one drawing executed incolor. Copies of this patent or patent application publication withcolor drawings will be provided by the Office upon request and paymentof the necessary fee.

FIG. 1 is an exemplary image from confocal laser scanning microscopydepicting phase inhomogeneity and dispersed solid particles, fromExample 6.

FIG. 2 is an exemplary image from confocal laser scanning microscopydepicting phase inhomogeneity from the one-pot version of Example 4.

FIG. 3 is a photomicrograph of a film produced from one-pot synthesis,in Example 7.

FIG. 4 is a photomicrograph of a film produced from two-pot synthesis,in Example 7.

FIG. 5 is a graph of electrochemical impedance spectra from an uncoatedand TiO₂-coated surface of 2024 Al, in Example 8.

FIG. 6(a) is an optical micrograph of an aluminum panel coated with amultiphase modular hydrophilic coating with corrosion inhibitors, beforesalt spray tests, in Example 9.

FIG. 6(b) is an optical micrograph of the aluminum panel coated with themultiphase modular hydrophilic coating that includes corrosioninhibitors, following 500 hours of a salt spray (1 M NaCl), in Example9.

FIG. 6(c) is an optical micrograph of the aluminum panel coated with themultiphase modular hydrophilic coating that does not include corrosioninhibitors, following 500 hours of a salt spray (1 M NaCl), in Example9.

DETAILED DESCRIPTION OF EMBODIMENTS OF THE INVENTION

The materials, compositions, structures, systems, and methods of thepresent invention will be described in detail by reference to variousnon-limiting embodiments.

This description will enable one skilled in the art to make and use theinvention, and it describes several embodiments, adaptations,variations, alternatives, and uses of the invention. These and otherembodiments, features, and advantages of the present invention willbecome more apparent to those skilled in the art when taken withreference to the following detailed description of the invention inconjunction with the accompanying drawings.

As used in this specification and the appended claims, the singularforms “a,” “an,” and “the” include plural referents unless the contextclearly indicates otherwise. Unless defined otherwise, all technical andscientific terms used herein have the same meaning as is commonlyunderstood by one of ordinary skill in the art to which this inventionbelongs.

Unless otherwise indicated, all numbers expressing conditions,concentrations, dimensions, and so forth used in the specification andclaims are to be understood as being modified in all instances by theterm “about.” Accordingly, unless indicated to the contrary, thenumerical parameters set forth in the following specification andattached claims are approximations that may vary depending at least upona specific analytical technique.

The term “comprising,” which is synonymous with “including,”“containing,” or “characterized by” is inclusive or open-ended and doesnot exclude additional, unrecited elements or method steps. “Comprising”is a term of art used in claim language which means that the named claimelements are essential, but other claim elements may be added and stillform a construct within the scope of the claim.

As used herein, the phrase “consisting of” excludes any element, step,or ingredient not specified in the claim. When the phrase “consists of”(or variations thereof) appears in a clause of the body of a claim,rather than immediately following the preamble, it limits only theelement set forth in that clause; other elements are not excluded fromthe claim as a whole. As used herein, the phrase “consisting essentiallyof” limits the scope of a claim to the specified elements or methodsteps, plus those that do not materially affect the basis and novelcharacteristic(s) of the claimed subject matter.

With respect to the terms “comprising,” “consisting of,” and “consistingessentially of,” where one of these three terms is used herein, thepresently disclosed and claimed subject matter may include the use ofeither of the other two terms, except when used in Markush groups. Thusin some embodiments not otherwise explicitly recited, any instance of“comprising” may be replaced by “consisting of” or, alternatively, by“consisting essentially of.”

This invention is predicated, at least in part, on the fabrication ofmaterials and coatings with solid functional particles. In particular,variations of this invention provide a synthesis strategy that enablesthe incorporation and segregation of functional particles intomicrophase-separated domains. This disclosure describes a new capabilityto fabricate multifunctional coatings with particles that usually cannotbe mixed or associated with each other, due to reactivity. By contrast,materials disclosed herein allow such particles to be contained in acoating, because particle segregation may be maintained until anexternal trigger is applied.

In particular, incompatible or reactive particles may be segregatedwithin the different phases of a coating, allowing for a latent,triggerable reaction. This technology enables the combination ofmultiple dissimilar particles in a single coating, which is notachievable with traditional synthesis techniques. The single coating hasmultiple phases in a microphase-separated network, wherein particles aredisposed selectively within those phases.

The materials described herein may be derived from specialty high-endprecursors or from cost-effective, commercially available materials. Themultiphase materials provided herein have many commercial applications,including but not limited to anti-corrosion, self-cleaning,self-healing, and flame-retardant coatings and materials.

For example, corrosion-resistant coatings may be provided. Someembodiments of the invention place reactive components into a coating,wherein the reactive components are later exploited, such as upon abreach or break in the coating, thereby providing on-demand corrosionprotection. Particle segregation within the coating enables the use ofmultiple species that are incompatible or reactive with each other,wherein a first species is separated from a second species until atrigger occurs to allow the first and second species to react with eachother.

Potential triggers include, but are not limited to, a break orstructural weakness in the coating caused physically or chemically;thermal stress break or weakening; hydrolytic stress; pH (acid and/orbase) stress; temperature, pH, mechanical force, and/or ultravioletrays. The trigger may be intentional or unintentional (e.g., caused byenvironmental factors).

Unless otherwise indicated, all references to “phases” in this patentapplication are in reference to solid phases. The solid phases aretypically polymeric and may melt or at least undergo a glass transitionat elevated temperatures. Reference to multiple solid phases in acomposition or microstructure means that there are at least two distinctchemical phases that are solid, without forming a solid solution orhomogeneous mixture.

As intended in this patent application, “phase inhomogeneity,”“inhomogeneous microstructure,” and the like mean that a multiphasemicrostructure is present in which there are at least two discretephases that are separated from each other. The two phases may be onediscrete solid phase in a continuous solid phase, two co-continuoussolid phases, or two discrete solid phases in a third continuous solidphase, for example. FIG. 1 is an exemplary optical image (confocal laserscanning microscopy) depicting phase inhomogeneity, from Example 6, forpurposes of illustration.

This patent application hereby expressly incorporates by referenceherein U.S. patent application Ser. No. 14/829,640 for “SEGMENTEDCOPOLYMER COMPOSITIONS AND COATINGS INCORPORATING THESE COMPOSITIONS”filed on Aug. 19, 2015 and published as U.S. Patent App. Pub. No.2016/0194574 on Jul. 7, 2016. This patent application hereby expresslyincorporates by reference herein U.S. patent application Ser. No.15/608,975 for “COMPOSITIONS AND METHODS FOR FABRICATING DURABLE,LOW-ICE-ADHESION COATINGS” filed on May 30, 2017 and published as U.S.Patent App. Pub. No. 2017/0267871 on Sep. 21, 2017.

Some embodiments utilize polymeric coating compositions containing atleast two phases that microphase-separate at microscopic length scales,including at a surface (such as a coating). In some embodiments, onephase contains a segmented urethane/urea copolymer composition thatincludes a fluoropolymer, a polyether, and a polyurethane.

Some embodiments employ fluoropolymers, without limitation of theinvention, as described in more detail herein. A preferred technique tocompatibilize fluoropolymers and hygroscopic materials is the use ofsegmented polyurethane or urea systems. These species demonstrate stronghydrogen bonding potential between them and as a result can createstrong associative forces between the chains. In order to produceelastomeric materials, regions of highly flexible and weakly interactingchains (soft segments) must be incorporated with strongly associatingelements (hard segments) and this can be provided in a segmentedcopolymerization scheme. Segmented copolymers provide a straightforwardsynthetic route toward block architectures using segments with vastlydiffering properties. Such synthesis results in chains that possessalternating hard and soft segments composed of regions of high urethanebond density and the chosen soft segment component (e.g., fluoropolymeror hygroscopic element), respectively. This covalent linkage ofdissimilar hard and soft blocks drives the systems to microphaseseparation and creates regions of flexible soft blocks surroundingregions of hard blocks. The associative forces among the hard segmentsprevent flow under stress and can produce elastomeric materials capableof displaying high elongation and tensile strength.

Some variations of this invention provide a multiphase polymercomposition comprising a first polymer material and a second polymermaterial that are chemically distinct, wherein the first polymermaterial and the second polymer material are microphase-separated on amicrophase-separation length scale from about 0.1 microns to about 500microns, wherein the multiphase polymer composition comprises firstsolid functional particles selectively dispersed within the firstpolymer material, and wherein the first solid functional particles arechemically distinct from the first polymer material and the secondpolymer material.

The average length scale of phase inhomogeneity may be from about 1micron to about 200 microns, such as from about 5 microns to about 100microns, for example. In various embodiments, the average length scaleof phase inhomogeneity is about, or at least about, 0.5, 1, 2, 3, 4, 5,10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 125, 150, 175, 200, or 250microns.

As intended herein, a “solid functional particle” means a material thatis a solid at a temperature of 25° C. and 1 bar pressure, in the form ofparticles such as with average particle size from about 50 nanometers toabout 500 microns. The term “functional” is intended only to distinguishfrom inert fillers, i.e. the solid functional particle is selected forone or more functions in the multiphase polymer composition, such as(but not limited to) anti-corrosion, self-healing, self-cleaning, orflame retardancy.

During synthesis, solid functional particles may be introduced at one ormore steps. Alternatively, or additionally, precursors of solidfunctional particles may be introduced, ultimately resulting in solidfunctional particles in the final multiphase polymer composition. Theprecursors may be non-solids, such as liquids or gels, that solidifyduring synthesis. Multiple precursors may be employed that chemicallyform solid functional particles during synthesis.

A wide range of concentrations of components may be present in themultiphase polymer composition. For example, the first polymer materialmay be from about 1 wt % to about 99 wt %, such as from about 5 wt % toabout 50 wt % of the multiphase polymer composition. The second polymermaterial may be from about 1 wt % to about 99 wt %, such as from about 5wt % to about 50 wt % of the multiphase polymer composition. The firstsolid functional particles may be from about 0.1 wt % to about 50 wt %of the multiphase polymer composition.

Within the first phase containing the first polymer material, the firstpolymer material may be from about 50 wt % to 100 wt %, such as about60, 70, 80, 90, 95, or 100 wt %. Within that first phase, the firstsolid functional particles may be from about 0.1 wt % to about 50 wt %of the total weight of the first polymer material and the first solidfunctional particles, or the total weight of the first phase. Theremainder of the material in the first phase may be polymeric (but adifferent polymer than the first polymer material) or non-polymeric(e.g., a filler).

Within a second phase containing the second polymer material, the secondpolymer material may be from about 50 wt % to 100 wt %, such as about60, 70, 80, 90, 95, or 100 wt %. Within that second phase, second solidfunctional particles may be from about 0 wt % to about 50 wt % of thetotal weight of the second polymer material and the second solidfunctional particles, or the total weight of the second phase. Theremainder of the material in the second phase may be polymeric (but adifferent polymer than the second polymer material) or non-polymeric(e.g., a filler).

In some variations, the multiphase polymer composition further comprisessecond solid functional particles selectively dispersed within thesecond polymer material, wherein the second solid functional particlesare chemically distinct from the first polymer material and the secondpolymer material. The second solid functional particles, when present,may be from about 0.1 wt % to about 50 wt % of the multiphase polymercomposition. The second solid functional particles, when present, may befrom about 0.1 wt % to about 50 wt % of the total weight of the secondpolymer material and the second solid functional particles, or the totalweight of applicable phase of the multiphase polymer composition.

In certain embodiments, the second solid functional particles, whenpresent, are essentially not contained at all within the first polymermaterial—that is, less than 0.5 wt % of the phase containing the firstpolymer material consists of the second solid functional particles. Inthese or other certain embodiments, the first solid functional particlesare essentially not contained at all within the second polymermaterial—that is, less than 0.5 wt % of the phase containing the secondpolymer material consists of the first solid functional particles.

The multiphase polymer composition may be characterized by a selectivityof solid functional particles contained within a certain phase, but notother phases, of a multiphase polymer composition.

The “first-particle selectivity” is defined as the fraction of firstsolid functional particles that are contained in the first polymerphase, relative to all first solid functional particles present in theoverall composition. The first-particle selectivity may be about 50% ormore, preferably about 75% or more, more preferably about 90% or more,and most preferably about 95% or more. In certain embodiments, thefirst-particle selectivity is about 99% or about 100% (i.e., essentiallyall of the first solid functional particles are contained in the firstpolymer phase). The first solid functional particles that are notcontained in the first polymer phase may be in the second polymer phasesand/or in other phases present (if any) in the multiphase polymercomposition.

Similarly, the “second-particle selectivity” is defined as the fractionof second solid functional particles that are contained in the secondpolymer phase, relative to all second solid functional particles presentin the overall composition. The second-particle selectivity may be about50% or more, preferably about 75% or more, more preferably about 90% ormore, and most preferably about 95% or more. In certain embodiments, thesecond-particle selectivity is about 99% or about 100% (i.e.,essentially all of the second solid functional particles are containedin the second polymer phase). The second solid functional particles thatare not contained in the second polymer phase may be in the firstpolymer phases and/or in other phases present (if any) in the multiphasepolymer composition.

By “first solid functional particles selectively dispersed within thefirst polymer material,” it is meant that the first-particle selectivityis at least 51%, preferably at least 75%, and more preferably at least90%. Similarly, by “second solid functional particles selectivelydispersed within the second polymer material,” it is meant that thesecond-particle selectivity is at least 51%, preferably at least 75%,and more preferably at least 90%.

Particles may be coated with one polymer phase that is itself present asan inclusion in another polymer phase (see for example FIG. 1). In thecontext of selectivity, when particles are coated with a first polymerphase and the entire coated particle is present as an inclusion in asecond polymer phase, those particles are deemed to be selective for(present in) the first polymer phase.

“Dispersed” solid functional particles means that those particles arepresent in the applicable polymer material as distinct particles orregions of material, not as a single layer or coating on top of oradjacent to that polymer material. The solid functional particles may bedispersed uniformly or non-uniformly within the polymer phase. As notedabove, the solid functional particles may be dispersed such that atleast some of the particles are coated with one polymer phase that isitself present as an inclusion in another polymer phase.

The first solid functional particles may have an average particle sizefrom about 50 nanometers to about 500 microns, for example. In variousembodiments, the first solid functional particles have an averageparticle size of about 0.1, 0.5, 1, 5, 10, 25, 50, 100, 200, 300, or 400microns. The first solid functional particles may be characterized byvarious ranges of particle sizes and particle-size distributions.

The second solid functional particles, when present, may have an averageparticle size from about 50 nanometers to about 500 microns, forexample. In various embodiments, the second solid functional particleshave an average particle size of about 0.1, 0.5, 1, 5, 10, 25, 50, 100,200, 300, or 400 microns. The second solid functional particles may becharacterized by various ranges of particle sizes and particle-sizedistributions.

The first solid functional particles may be dissolvable in water or anaqueous solvent. Alternatively, or additionally, the first solidfunctional particles may be dissolvable in an organic solvent. Any ofthese solvents may be environmental solvents, i.e. fluids derived fromthe local environment, such as rain, ocean spray, melted snow or ice,humidity, fuel, cleaning fluid, hydraulic fluid, or anti-icing fluid.

In some embodiments, the first solid functional particles are capable ofreacting with the second polymer material, in response to anenvironmental input selected from the group consisting of ultravioletlight, change in temperature, change in pressure, environmentalsolvents, change in humidity, change in pH, and combinations thereof. Anexemplary combination of environmental inputs is prolonged exposure toultraviolet light, causing local extremes in temperature or pH, whichcould lead to chemical degradation or flammability. Another exemplarycombination is a change in pressure (force) causing a coating breach,followed by exposure to an environmental solvent that allows the firstsolid functional particles and the second polymer material to contacteach other and then react.

The environmental input may act as a trigger to cause a physical changein the multiphase polymer composition, such as formation of a surfacedefect or a break in the bulk material. The environmental input may actas a trigger to cause a chemical change in the multiphase polymercomposition, such as an alteration in chemical composition or adisruption of chemical phase stability. The trigger may be intentionalor unintentional. The trigger, in turn, may allow the first solidfunctional particles to be transported (e.g., by convection ordiffusion) from the first polymer material to the second polymermaterial, where reaction may occur between the solid functionalparticles and the polymer material. The mass transport of first solidfunctional particles may be aided by a fluid, such as water or anotherenvironmental solvent. Also note that in certain embodiments, the secondpolymer material (e.g., when in the form of inclusions) is transportedto the location of the first solid functional particles contained withthe first polymer material. In some embodiments, solid functionalparticles are not segregated to a surface or interface via particlepreference for the air interface.

The first solid functional particles may be in close physical proximitywith the second solid functional particles (when present), the secondpolymer material, and/or a substrate surface. The physical proximitywill generally be on the same length scale as the microphase separation,i.e. from about 0.1 microns to about 500 microns (see Example 6), sincethe solid functional particles are selectively dispersed in the phasesthat are microphase-separated. When the multiphase polymer material isapplied to a substrate, the solid functional particles will generally bein close physical proximity to the substrate since those particles arepresent throughout the bulk of the material, not just at the outersurface.

When the function of the solid functional particles is to be triggeredwith a break in a coating (in some embodiments), the break may varywidely in width, such as from about 10 microns to about 10 centimeters,e.g. about 100 microns to about 1 centimeter. The length of the break isvirtually unlimited, depending on the specific coating application, butcan be for example from about 100 microns to about 1 meter or more.

In some embodiments, the multiphase polymer composition is disposed on asurface, and the first solid functional particles are capable ofreacting with the surface, in response to an environmental inputselected from the group consisting of ultraviolet light, change intemperature, change in pressure, environmental solvents, change inhumidity, change in pH, and combinations thereof. The same types oftriggers mentioned above apply to reaction of solid functional particleswith the surface. The mass transport of first solid functional particlesto the surface may be aided by a fluid, such as water or anotherenvironmental solvent.

When second solid functional particles are present, the first solidfunctional particles and the second solid functional particles may becapable of reacting with each other in response to an environmentalinput selected from the group consisting of ultraviolet light, change intemperature, change in pressure, environmental solvents, change inhumidity, change in pH, and combinations thereof. The same types oftriggers mentioned above apply to reaction of first and second solidfunctional particles with each other. The mass transport of solidfunctional particles to find each other may be aided by a fluid, such aswater or another environmental solvent. Also note that in variousembodiments, the first solid functional particles may be transportedwhile the second solid functional particles remain stationary in thesecond polymer material, or vice-versa. In some embodiments, both thefirst solid functional particles and the second solid functionalparticles are transported, at least to some extent, out of theirrespective phases.

In some embodiments, the second solid functional particles areunreactive with the first solid functional particles under conditions ofuse of the multiphase polymer composition, such as at ambienttemperature, pressure, and humidity.

In preferred embodiments, the first solid functional particles areunreactive with the first polymer material, and the second solidfunctional particles (if present) are unreactive with the second polymermaterial. However, the invention is not limited to these embodiments;the first and second solid functional particles may be capable ofreacting with the first and second polymer material, respectively—i.e.the material in which the respective solid functional particles aredispersed—in response to an environmental input.

When second solid functional particles are present, they may be capableof reacting with the first polymer material, in response to anenvironmental input selected from the group consisting of ultravioletlight, change in temperature, change in pressure, environmentalsolvents, change in humidity, change in pH, and combinations thereof.This is analogous to reaction of first solid functional particles withthe second polymer material, described above.

In some embodiments, the multiphase polymer composition is disposed on asurface, and the second solid functional particles are included andcapable of reacting with the surface, in response to an environmentalinput selected from the group consisting of ultraviolet light, change intemperature, change in pressure, environmental solvents, change inhumidity, change in pH, and combinations thereof. This is also analogousto reaction of first solid functional particles with the surface,described above. It will be appreciated that many combinations ofreactions and locations of reactions are possible.

The second solid functional particles may be dissolvable in water or anaqueous solvent. Alternatively, or additionally, the second solidfunctional particles may be dissolvable in an organic solvent. Any ofthese solvents may be environmental solvents, i.e. fluids derived fromthe local environment, such as rain, ocean spray, melted snow or ice,humidity, fuel, cleaning fluid, hydraulic fluid, or anti-icing fluid.

The first solid functional particles may include inorganic particles,organic particles, or a combination thereof. The second solid functionalparticles, when present, may include inorganic particles, organicparticles, or a combination thereof.

The first solid functional particles may include oxidizing agents,reducing agents, or a combination thereof. The second solid functionalparticles, when present, may include oxidizing agents, reducing agents,or a combination thereof.

The first solid functional particles may be selected from the groupconsisting of metals, metal oxides (or other oxides, such as organicoxides), ceramics, salts, polymers, and combinations thereof. The firstsolid functional particles may be thermally stable or thermallyunstable, such as thermally unstable at temperatures exceeding atemperature selected from 25° C. to 50° C.

The second solid functional particles, when present, may be selectedfrom the group consisting of metals, metal oxides (or other oxides, suchas organic oxides), ceramics, salts, polymers, and combinations thereof.The second solid functional particles may be thermally stable orthermally unstable, such as thermally unstable at temperatures exceedinga temperature selected from 25° C. to 50° C.

The first solid functional particles may be surface-treated to enhancechemical compatibility with the first polymer material. The second solidfunctional particles, when present, may be surface-treated to enhancechemical compatibility with the second polymer material. Surfacetreatment may adjust properties such as hydrophobicity, hydrophilicity,surface tension, polarity, and solubility.

In various embodiments, the first polymer material and the secondpolymer material are independently selected from the group consisting ofpolyesters, polyethers, polyacrylates, polymethacrylates, polyepoxides,polysiloxanes, cellulosic polymers, and combinations thereof.

Polyesters and polyethers may be selected from the group consisting ofperfluoropolyethers, polyfluoroacrylates, polyfluorosiloxanes,polyvinylidene fluoride, polytrifluoroethylene, poly(oxymethylene),poly(ethylene glycol), poly(propylene oxide), poly(tetrahydrofuran),poly(glycolic acid), poly(caprolactone), poly(ethylene adipate),poly(hydroxyl butyrate), poly(hydroxyl alkanoate), and combinationsthereof.

Polyacrylates, polymethacrylates, polyepoxides, polysiloxanes, andcellulosic polymers may be selected from the group consisting ofpolymethylmethacrylate, poly(acrylic acid), poly(2-hydroxyethylmethacrylate), poly(vinyl imidazole), poly(2-methyl-2-oxazoline),poly(2-ethyl-2-oxazoline), poly(vinylpyrolidone), polydimethylsiloxane,cellulose, cellulose hydrogels, methyl cellulose, carboxymethylcellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, andcombinations thereof.

In some coatings, one of the first-material phase and thesecond-material phase is hydrophobic, and the other is hydrophilic. Inthese or other embodiments, one of the first-material phase and thesecond-material phase is hydrophobic, and the other is hygroscopic. Inthese or other embodiments, one of the first-material phase and thesecond-material phase is hygroscopic, and the other comprises alow-surface-energy polymer having a surface energy between about 5 mJ/m²to about 50 mJ/m².

“Hygroscopic” means that the material is capable of attracting andholding water molecules from the surrounding environment. The wateruptake of various polymers is described in Thijs et al., “Water uptakeof hydrophilic polymers determined by a thermal gravimetric analyzerwith a controlled humidity chamber”, J. Mater. Chem. (17) 2007,4864-4871, which is hereby incorporated by reference herein. In someembodiments, the hygroscopic material is characterized by a waterabsorption capacity, at 90% relative humidity and 30° C., of at least 5,10, 15, 20, 25, 30, 35, 40, 45, or 50 wt % increase due to water uptake.

In some embodiments, the hygroscopic material is selected from the groupconsisting of poly(acrylic acid), poly(ethylene glycol),poly(2-hydroxyethyl methacrylate), poly(vinyl imidazole),poly(2-methyl-2-oxazoline), poly(2-ethyl-2-oxazoline),poly(vinylpyrolidone), cellulose, modified cellulose, carboxymethylcellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, methylcellulose, hydrogels, PEG diacrylate or monoacrylate, and combinationsthereof.

A “low-surface-energy polymer” means a polymer with a surface energy ofno greater than 50 mJ/m². In some embodiments, the low-surface-energypolymer is a fluoropolymer, such as selected from the group consistingof polyfluoroethers, perfluoropolyethers, polyfluoroacrylates,polyfluorosiloxanes, polytetrafluoroethylene (PTFE), polyvinylidenedifluoride (PVDF), polyvinylfluoride (PVF), polychlorotrifluoroethylene(PCTFE), copolymers of ethylene and trifluoroethylene, copolymers ofethylene and chlorotrifluoroethylene, and combinations thereof.

In some embodiments, one of the first polymer material or the secondpolymer material is a continuous matrix, and the other of the firstpolymer material or the second polymer material is a plurality ofinclusions, dispersed within the continuous matrix. Either thecontinuous matrix or the inclusions may be the first polymer materialcontaining the first solid functional particles, and the continuousmatrix or inclusions that do not contain the first solid functionalparticles optionally contain second solid functional particles.

The inclusions may be characterized as templates, domains, or regions(such as phase-separated regions). The inclusions are not a single,continuous framework in the coating. Rather, the inclusions arediscrete, non-continuous and dispersed in the continuous matrix (see forexample FIGS. 1 and 2). The inclusions may be dispersed uniformly withinthe continuous matrix. In some embodiments, the inclusions and thecontinuous matrix are covalently connected in a block copolymer, inwhich the inclusions and the continuous matrix are distinct phases ofthe block copolymer, such as a segmented block copolymer.

As intended herein, a “block copolymer” means a copolymer containing alinear arrangement of blocks, where each block is defined as a portionof a polymer molecule in which the monomeric units have at least oneconstitutional or configurational feature absent from the adjacentportions. Several types of block copolymers are generally possible,including AB block copolymers, ABA block copolymers, ABC blockcopolymers, segmented block copolymers, and random copolymers. Segmentedblock copolymers are preferred, in embodiments of the invention.

When the multiphase polymer composition contains inclusions within acontinuous matrix, the continuous matrix may be from about 5 wt % toabout 95 wt %, such as from about 10 wt % to about 50 wt % of themultiphase polymer composition. The inclusions may be from about 1 wt %to about 90 wt %, such as from about 10 wt % to about 50 wt % of themultiphase polymer composition. Within the continuous matrix, thepolymer may be from about 50 wt % to 100 wt %, such as about 60, 70, 80,90, 95, or 100 wt %. Within the inclusions, the other polymer may befrom about 50 wt % to 100 wt %, such as about 60, 70, 80, 90, 95, or 100wt %.

The continuous matrix and the inclusions may be covalently bonded witheach other, directly or via reactive species contained within and/orbetween the continuous matrix and the inclusions. In some embodiments,the reactive species include an isocyanate species and an alcohol oramine with functionality of 2 or greater. An isocyanate species may beselected from the group consisting of 4,4′-methylenebis(cyclohexylisocyanate), hexamethylene diisocyanate, cycloalkyl-based diisocyanates,tolylene-2,4-diisocyanate, 4,4′-methylenebis(phenyl isocyanate),isophorone diisocyanate, and combinations or derivatives thereof. Inthese or other embodiments, the reactive species includes an epoxy andan alcohol, amine, or thiol with functionality of 2 or greater.

In some embodiments, the continuous matrix and the inclusions arecovalently bonded with each other via reactive species, in a segmentedblock copolymer containing first soft segments and second soft segments,wherein one of the continuous matrix or the inclusions contain the firstsoft segments, and wherein the other of the continuous matrix or theinclusions contain the second soft segments.

Some embodiments can be understood with reference to FIG. 1, as anexemplary microphase-separated multiphase polymer composition (Example6). The scale bar is 100 μm. The phase inhomogeneity can becharacterized by a length scale associated with a discrete phase 120.For example, the length scale of phase inhomogeneity may refer to theaverage size (e.g., effective diameter) of discrete inclusions 120dispersed in a continuous phase 110. The selected (for illustration)discrete phase inclusions 120 labeled in FIG. 1 have an effectivediameter of about 50-100 microns; generally the inclusions have aneffective diameter of about 1 to 100 microns in this image. The lengthscale of phase inhomogeneity may refer to the average center-to-centerdistance between nearest-neighbor inclusions of the same phase 120. InFIG. 1, the center-to-center distance varies from about 5 microns toabout 50 microns. The length scale of phase inhomogeneity mayalternatively refer to the average separation distance betweennearest-neighbor regions of the discrete (e.g., droplets) phase 120,i.e. the size of the continuous phase 110 regions. In FIG. 1, theseparation distance varies from about 5 microns to about 200 microns.The average length scale of phase inhomogeneity is in the range of about1 micron to about 200 microns in FIG. 1.

The average length scale of phase inhomogeneity may generally be fromabout 0.1 microns to about 500 microns, which in this disclosure is alsogenerally referred to as “microphase separation.” In some embodiments,the average length scale of phase inhomogeneity is from about 0.5microns to about 100 microns, such as about 1 micron to about 50microns. In various embodiments, the average length scale of phaseinhomogeneity is about 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1,2, 3, 4, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 60, 70, 80, 90, 100,150, 200, 250, 300, 350, 400, 450, or 500 microns, including anyintermediate values not explicitly recited, and ranges starting, ending,or encompassing such intermediate values. These are average values,noting that a portion of phase inhomogeneity may be present on a lengthscale less than 0.1 micron or greater than 500 microns (e.g., about 1000microns), with the overall average falling in the range of 0.1-500microns.

Generally, the multiphase polymer composition may contain a segmentedblock copolymer, wherein the first polymer material consists essentiallyof first soft segments of the segmented block copolymer, and wherein thesecond polymer material consists essentially of second soft segments ofthe segmented block copolymer.

In certain embodiments, the segmented copolymer composition comprises:

(a) one or more the first soft segments selected from fluoropolymershaving an average molecular weight from about 500 g/mol to about 10,000g/mol, wherein the fluoropolymers are (α,ω)-hydroxyl-terminated and/or(α,ω)-amine-terminated;

(b) one or more the second soft segments selected from polyesters orpolyethers, wherein the polyesters or polyethers are(α,ω)-hydroxyl-terminated and/or (α,ω)-amine-terminated, wherein themolar ratio of the second soft segments to the first soft segments isoptionally less than 2.0;

(c) one or more isocyanate species, or a reacted form thereof,possessing an isocyanate functionality of 2 or greater; and

(d) one or more polyol or polyamine chain extenders or crosslinkers, ora reacted form thereof.

The fluoropolymer may be selected from the group consisting ofpolyfluoroethers, perfluoropolyethers, polyfluoroacrylates,polyfluorosiloxanes, polytetrafluoroethylene, polyvinylidene difluoride,polyvinylfluoride, polychlorotrifluoroethylene, copolymers of ethyleneand trifluoroethylene, copolymers of ethylene andchlorotrifluoroethylene, and combinations thereof.

The fluoropolymers may be present in the triblock structure:

wherein:X, Y═CH₂—(O—CH₂—CH₂)_(p)-T, and X and Y are independently selected;p=1 to 50;T is a hydroxyl or amine terminal group;m=1 to 100; andn=0 to 100.

It is noted that (α,ω)-terminated polymers are terminated at each end ofthe polymer. The α-termination may be the same or different than thew-termination. Also it is noted that in this disclosure,“(α,ω)-termination” includes branching at the ends, so that the numberof terminations may be greater than 2 per polymer molecule. The polymersherein may be linear or branched, and there may be various terminationsand functional groups within the polymer chain, besides the end (α,ω)terminations.

In some embodiments, the molar ratio of the second soft segments to thefirst soft segments is from about 0.1 to about 1.5. In variousembodiments, the molar ratio of the second soft segments to the firstsoft segments is about 0.05, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8,0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, or 1.95.

In this description, “polyurethane” is a polymer comprising a chain oforganic units joined by carbamate (urethane) links, where “urethane”refers to N(H)—(C═O)—O—. Polyurethanes are generally produced byreacting an isocyanate containing two or more isocyanate groups permolecule with one or more polyols containing on average two or morehydroxyl groups per molecule, in the presence of a catalyst.

Polyols are polymers in their own right and have on average two or morehydroxyl groups per molecule. For example, α,ω-hydroxyl-terminatedperfluoropolyether is a type of polyol.

“Isocyanate” is the functional group with the formula —N═C═O. For thepurposes of this disclosure, O—C(═O)—N(H)—R is considered a derivativeof isocyanate.

“Polyfluoroether” refers to a class of polymers that contain an ethergroup—an oxygen atom connected to two alkyl or aryl groups, where atleast one hydrogen atom is replaced by a fluorine atom in an alkyl oraryl group.

“Perfluoropolyether” (PFPE) is a highly fluorinated subset ofpolyfluoroethers, wherein all hydrogen atoms are replaced by fluorineatoms in the alkyl or aryl groups.

“Polyurea” is a polymer comprising a chain of organic units joined byurea links, where “urea” refers to N(H)—(C═O)—N(H)—. Polyureas aregenerally produced by reacting an isocyanate containing two or moreisocyanate groups per molecule with one or more multifunctional amines(e.g., diamines) containing on average two or more amine groups permolecule, optionally in the presence of a catalyst.

A “chain extender or crosslinker” is a compound (or mixture ofcompounds) that link long molecules together and thereby complete apolymer reaction. Chain extenders or crosslinkers are also known ascuring agents, curatives, or hardeners. In polyurethane/urea systems, acurative is typically comprised of hydroxyl-terminated oramine-terminated compounds which react with isocyanate groups present inthe mixture. Diols as curatives form urethane linkages, while diaminesas curatives form urea linkages. The choice of chain extender orcrosslinker may be determined by end groups present on a givenprepolymer. In the case of isocyanate end groups, curing can beaccomplished through chain extension using multifunctional amines oralcohols, for example. In some embodiments, the prepolymer has excesshydroxyl and/or amine functional groups and thus is curable with anisocyanate curing agent.

Chain extenders or crosslinkers can have an average functionalitygreater than 2 (such as 2.5, 3.0, or greater), i.e. beyond diols ordiamines. In some embodiments, polymeric forms of polyol chain extendersor crosslinkers are utilized, typically hydrocarbon or acrylic backboneswith hydroxyl groups distributed along the side groups. Thesecrosslinkers typically possess a functionality of much greater than 2.The one or more chain extenders or crosslinkers (or reaction productsthereof) may be present in a concentration, in the segmented copolymercomposition, from about 0.01 wt % to about 25 wt %, such as about 0.05wt % to about 10 wt %.

The polyol or polyamine chain extenders or crosslinkers may be selectedfrom the group consisting of 1,3-butanediol, 1,4-butanediol,1,3-propanediol, 1,2-ethanediol, diethylene glycol, triethylene glycol,tetraethylene glycol, propylene glycol, dipropylene glycol, tripropyleneglycol, neopentyl glycol, 1,6-hexanediol, 1,4-cyclohexanedimethanol,ethanol amine, diethanol amine, methyldiethanolamine,phenyldiethanolamine, glycerol, trimethylolpropane, 1,2,6-hexanetriol,triethanolamine, pentaerythritol, ethylenediamine, 1,3-propanediamine,1,4-butanediamine, diethyltoluenediamine, dimethylthiotoluenediamine,isophoronediamine, diaminocyclohexane,N,N,N′,N′-tetrakis(2-hydroxypropyl) ethylenediamine, and homologues,derivatives, or combinations thereof. In certain embodiments, the polyolor polyamine chain extenders or crosslinkers possess an averagefunctionality of about 3 or greater.

The isocyanate species may be selected from the group consisting of4,4′-methylenebis(cyclohexyl isocyanate), hexamethylene diisocyanate,cycloalkyl-based diisocyanates, tolylene-2,4-diisocyanate,4,4′-methylenebis(phenyl isocyanate), isophorone diisocyanate, andcombinations or derivatives thereof.

Following a suitable chemical reaction, the segmented copolymercomposition contains, in a hard segment, the reacted form of the one ormore isocyanate species, combined with the reacted form of the one ormore polyol or polyamine chain extenders or crosslinkers. In someembodiments, the hard segment is present in an amount from about 5 wt %to about 60 wt %, based on total weight of the composition.

In a segmented copolymer composition, a total content of one or morefirst soft segments and one or more second soft segments is present inan amount of from about 40% by weight to about 90% by weight, based on atotal weight percent of the composition. The composition furthercomprises one or more hard segments present in an amount of from about15% by weight to about 50% by weight, based on the total weight percentof the composition.

Optionally, the multiphase polymer composition may further include oneor more additional components selected from a particulate filler, apigment, a dye, a plasticizer, a flame retardant, a colorant, a UVabsorber, a defoamer, a plasticizer, a viscosity modifiers, a densitymodifier, a catalyst, a scavenger, or a combination thereof. Theparticulate filler may be selected from the group consisting of silica,alumina, silicates, talc, aluminosilicates, barium sulfate, mica,diatomite, calcium carbonate, calcium sulfate, carbon, wollastonite, andcombinations thereof.

In some embodiments, the multiphase polymer composition further includesa solid-state lubricant, dispersed in one phase or dispersed throughoutthe polymer, distinct from the functional solid particles. Solid-statelubricants may be selected from the group consisting of graphite,graphene, molybdenum disulfide, tungsten disulfide, hexagonal boronnitride, poly(tetrafluoroethylene), and combinations thereof. Thesolid-state lubricants may be particles having outer surfaces coatedwith a metal selected from the group consisting of cadmium, lead, tin,zinc, copper, nickel, and combinations or alloys thereof.

Optionally, the multiphase polymer composition, when applied to asubstrate, further includes an adhesion promoter within its compositionand/or added to the substrate. The adhesion promoter may be selectedfrom the group consisting of a silane, a polysilane, a silazane, apolysilazane, an epoxy-based material, and combinations thereof. Otheradhesion promoters may be utilized. The adhesion promoter shouldincrease the chemical and/or physical adhesion of the coating material,compared to the surface without the adhesion promoter. The necessity andchoice of adhesion promoter will depend at least on the material of thebare surface (e.g., aluminum, carbon fibers, etc.).

Phase inhomogeneity typically causes opaque coatings due to thescattering of light. Scattering of light including visible wavelengthsin the bulk of a material is governed by changes in the index ofrefraction through the medium. Variations in refractive index at lengthscales near the wavelength of the propagating radiation will tend toscatter those wavelengths more effectively (Mie scattering), resultingin an opaque or white appearance for a coating. With visible lighthaving a wavelength range of about 400-700 nm, a clear or transparentcoating must typically keep variations in index of refraction belowabout 50 nm in length. As phase inhomogeneities increase in lengthscale, the opacity of the material rises. Phase inhomogeneities withaverage length scale from 0.1 μm to 500 μm are expected to drivesignificant scattering in the material, leading to opaque structuresabove 25 μm in thickness—unless the multiple phases happen to berefractive index-matched. See Althues et al., “Functional inorganicnanofillers for transparent polymers”, Chem. Soc. Rev., 2007, 36,1454-1465, which is hereby incorporated by reference herein for itsteaching that materials with inhomogeneity below 50 nm will tend to beclear, and materials with inhomogeneity above 50 nm (0.05 μm) will tendto be more opaque. The coating may be characterized by a coatingtransparency of less than 70% average light transmission in thewavelength range of 400 nm to 700 nm, through a 1-millimeter-thickcoating sample (defined test depth), or a transparency less than about65%, 60%, 55%, 50%, 45%, 40%, 35%, 30%, 25%, 20%, 15%, or 10% averagelight transmission in the wavelength range of 400 nm to 700 nm, througha 1-millimeter-thick coating sample.

The inhomogeneity exists throughout the material, in both planar anddepth dimensions. That it, the microphase separation is not just asurface effect and will be present even if the coatings are eroded overtime. The coating function is retained even after abrasion (for whateverreason) of the top layer of the material. Relatively thick coatingsoffer good durability and mechanical properties, such as impactresistance, while being relatively lightweight. In certain embodiments,a coating has a thickness from about 10 microns to about 10 millimeters.The overall thickness of the final material or coating may be from about1 μm to about 1 cm or more, such as about 5 μm, 10 μm, 20 μm, 25 μm, 30μm, 40 μm, 50 μm, 75 μm, 100 μm, 200 μm, 300 μm, 400 μm, 500 μm, 750 μm,1 mm, 2 mm, 3 mm, 4 mm, 5 mm, 6 mm, 7 mm, 8 mm, 9 mm, 10 mm, or more. Ifdesired, a coating may have a varying thickness, such as greaterthickness at high surface curvature, for example.

In various embodiments, the material is a coating and/or is present at asurface of an object or region. In principle, the material could bepresent within a bulk region of an object or part.

The multiphase polymer composition may be present in or as a coating,such as (but not limited to) an anti-corrosion coating applied to ametallic substrate. Certain embodiments with respect to anti-corrosioncoatings will now be described, and it will be understood that the sameor similar principles may be applied to other coatings, such as (but notlimited to) self-cleaning, self-lubricating, self-healing, orflame-retardant coatings.

Anti-Corrosion Coatings

Corrosion converts a metal to a more chemically stable form, such as itsoxide, hydroxide, or sulfide. Corrosion gradually destroys metals bychemical and/or electrochemical reaction with their environment.Rusting, the formation of iron oxides, is a well-known example ofelectrochemical corrosion. Corrosion can also occur in materials otherthan metals, such as ceramics or polymers. Corrosion degrades the usefulproperties of materials and structures including strength, appearance,and permeability to liquids and gases. Many structural alloys corrodemerely from exposure to moisture in air, but the process can be stronglyaffected by exposure to certain substances. Corrosion can beconcentrated locally to form a pit or crack, or it can extend across awide area more or less uniformly corroding the surface. Becausecorrosion is a diffusion-controlled process, it occurs on exposedsurfaces. Therefore, anti-corrosion coatings on those surfaces are ofwide interest commercially.

A particular application of interest includes, without limitation,corrosion resistant primers or base coats. Effective anti-corrosioncoatings on the market contain hexavalent chromate, Cr⁶⁺, which istoxic, is an environmental hazard, and is being phased out of mostcommercial coatings due to existing and pending regulations.

In a specific embodiment, a nontoxic form of chromium, chromium(III)oxide (Cr₂O₃), may be used with an oxidant (e.g., KMnO₄) to form Cr³⁺and/or Cr⁶⁺ in situ (such as in a crack or break in the coating) andonly when needed, greatly reducing the use and necessary disposal ofhazardous Cr⁶⁺ compounds.

A variety of possible corrosion inhibitor compounds may be incorporatedinto multiphase polymer structures, including (i) redox reaction-typeinhibitors (which form a barrier layer from a redox reaction), such asthose with oxo-metal anion precursors (e.g., CrO⁴⁻ or MnO⁴⁻); (ii)hydrolysis reaction-type inhibitors (which also form a barrier layerfrom a hydrolysis reaction), such as those with metal precursors (e.g.,TiF₆ ²⁻ or Ti sol-gels); (iii) anodic polarization-type inhibitors(which protect the surface using a sacrificial species), such as anodicmetal particles (e.g., Mg particles); (iv) adsorbate-type inhibitors(which form a barrier layer from molecularly adsorbed species), such asorganic inhibitors; and (v) combinations thereof.

In certain embodiments, a single-component corrosion inhibitor isintroduced into one phase of a multiphase polymer composition, while theother phase(s) is (are) tailored or optimized for other properties(e.g., strength, elasticity, etc.).

Some variations of the invention provide an anti-corrosion compositioncomprising a first polymer material and a second polymer material thatare chemically distinct, wherein the first polymer material and thesecond polymer material are microphase-separated on amicrophase-separation length scale from about 0.1 microns to about 500microns, wherein the multiphase polymer composition comprises firstcorrosion-inhibitor particles or precursors selectively dispersed withinthe first polymer material, wherein the multiphase polymer compositionoptionally further comprises second corrosion-inhibitor particles orprecursors selectively dispersed within the second polymer material, andwherein the first corrosion-inhibitor particles or precursors and thesecond corrosion-inhibitor particles or precursors are chemicallydistinct from the first polymer material and the second polymermaterial.

Any known corrosion inhibitors may be employed as corrosion-inhibitorparticles, or as part of corrosion-inhibitor particles. Corrosioninhibitors may be selected based on the material to be protected(usually a metal or metal alloy) and on the potential corrosive agent(s)to be neutralized. Corrosive agents include (but are not limited to)oxygen, carbon dioxide, hydrogen sulfide. Oxygen may be removed byreductive inhibitors, such as amines and hydrazines, which convertoxygen to water, which is generally benign. Related inhibitors of oxygencorrosion are hexamine, phenylenediamine, dimethylethanolamine, andtheir derivatives. Antioxidants such as sulfite and ascorbic acid may beused. Some corrosion inhibitors, such as benzotriazole, form apassivating coating on the surface by chemisorption. Other exemplarycorrosion inhibitors include zinc phosphate, zinc dithiophosphates,benzalkonium chloride, and compounds derived from tannic acid or zincsalts of organonitrogens.

In some embodiments, the first corrosion-inhibitor particles orprecursors and/or the second corrosion-inhibitor particles or precursors(when present) are selected from the group consisting of redoxreaction-type inhibitors, hydrolysis reaction-type inhibitors, anodicpolarization-type inhibitors, adsorbate-type inhibitors, andcombinations thereof.

In some embodiments, a corrosion-inhibitor particle or precursor is aprecursor that itself is not necessarily effective to prevent corrosion,but which may be converted to a corrosion inhibitor following a reactioncaused by an environmental trigger, which may be intentional orunintentional.

In some embodiments, the corrosion inhibitor is present in the form ofmultiple precursors that are physically separated in the first andsecond particles contained in the first polymer material and secondpolymer material, respectively. These precursors may come together inresponse to an environmental trigger, and react to form a corrosioninhibitor or anti-corrosion layer.

In certain exemplary embodiments, the first corrosion-inhibitorparticles or precursors include ammonium hexafluorotitanate, and thesecond corrosion-inhibitor particles or precursors include boric acid.In these embodiments, the second corrosion-inhibitor particles orprecursors may further include a salt, such as sodium chloride. In theseor other exemplary embodiments, the first corrosion-inhibitor particlesor precursors include chromium(III) oxide, and the secondcorrosion-inhibitor particles or precursors include potassiumpermanganate.

In some embodiments employing the second corrosion-inhibitor particlesor precursors, the first corrosion-inhibitor particles or precursors andthe second corrosion-inhibitor particles or precursors are capable ofreacting with each other in response to an environmental input selectedfrom the group consisting of ultraviolet light, change in temperature,change in pressure, environmental solvents, change in humidity, changein pH, and combinations thereof.

In some embodiments employing the second corrosion-inhibitor particlesor precursors, the anti-corrosion composition is disposed on ametal-containing substrate, wherein the first corrosion-inhibitorparticles or precursors and the second corrosion-inhibitor particles orprecursors are capable of reacting with each other to form a passivationcoating or anti-corrosion layer on the metal-containing substrate. Ananti-corrosion layer reduces the corrosion potential of the underlyingmetal-containing substrate.

Methods

Some preferred variations segregate reactive species during synthesis,i.e. particles that are reactive with each other are kept physicallyseparated during the initial synthesis, allowing a selected polymerphase to coat the reactive particles. Two distinct portions of thepolymer, e.g. first and second soft segments, are then combined suchthat the particles remain in different phases as the two incompatiblephases separate, while maintaining the mechanical integrity of theresulting coating. Incorporation of reactive species into the coatingenables the species to be isolated (i.e., not in chemical contact), yetbe in close physical proximity for an externally triggered reaction.After coating damage, the reactive particles may be passively activatedby environmental changes including, but not limited to, temperature, pH,mechanical force, and/or ultraviolet rays.

In the case of segmented copolymers, the initial prepolymer reactionpreferably takes place in separate reaction vessels to form first andsecond soft segments. These separate reaction products are then combinedand may be applied to a surface in the presence of a curative to resultin a multiphase polymer coating.

Segmented copolymers are typically created by combining a flexibleoligomeric soft segment terminated with alcohol or amine reactive groupsand a multifunctional isocyanate. When the isocyanate is provided inexcess to the alcohol/amine reactive groups, a viscous prepolymermixture with a known chain length distribution is formed. This can thenbe cured to a high-molecular-weight network through the addition ofamine or alcohol reactive groups to bring the ratio of isocyanate toamine/alcohol groups to unity. The product of this reaction is a chainbackbone with alternating soft segments composed of flexible oligomersand hard segments comprised of the reaction product of low molecularweight isocyanates and alcohol/amines. Due to the chemical immiscibilityof these two phases, the material will typically phase separate on thelength scale of these individual blocks, creating a microstructure offlexible regions adjacent to rigid segments strongly associated throughhydrogen bonding of the urethane/urea moieties. This combination offlexible and associated elements typically produces a physicallycrosslinked elastomeric material. Incorporation of two or more softsegment oligomer blocks into a segmented polyurethane system causes theseparate oligomer blocks to microphase-separate.

A significant difference in the synthesis, according to someembodiments, is the segregation of the two soft segments during themajority of the prepolymer formation. This allows potentially reactiveparticles to be incorporated into each phase of the polymer, withminimal particle mixing, but placing them in close physical proximityfor a latent triggered reaction. The initial prepolymer reaction may beperformed in two separate reaction pots, keeping the soft segments andthe chosen particle additives physically separated. After each softsegment is sufficiently reacted, the two pots may be combined into onepot, mixed for a short time, and finally through the addition of amineor alcohol reactive groups the coating may be cured to ahigh-molecular-weight network.

An advantage of this synthesis technique is the unique structure thatforms, which contains segregated incompatible or reactive particles in asingle coating. The proximity advantage allows the particles themselvesto be chosen to perform a particular function when they are combined andreact after a defined trigger (such as a break in the coating) to form aprotective (e.g., passivating) coating.

Variations of the invention also provide a method of making a multiphasepolymer composition, the method comprising:

(a) in a first reaction container, synthesizing a first polymer materialfrom first-polymer starting components;

(b) in a second reaction container, synthesizing a second polymermaterial from second-polymer starting components, wherein the secondpolymer material is chemically distinct from the first polymer material;

(c) introducing a plurality of first solid functional particles into thefirst reaction container, to dispose the first solid functionalparticles in the first polymer material, wherein the first solidfunctional particles are chemically distinct from the first polymermaterial and the second polymer material;

(d) optionally introducing a plurality of second solid functionalparticles into the second reaction container, to disperse the secondsolid functional particles in the second polymer material;

(e) providing reactive species capable of covalently bonding the firstpolymer material with the second polymer material; and

(f) combining the first polymer material, the second polymer material,and the reactive species to covalently bond the first polymer materialwith the second polymer material, thereby generating a multiphasepolymer composition,

wherein the multiphase polymer composition comprises the first solidfunctional particles selectively dispersed within the first polymermaterial, and wherein the first polymer material and the second polymermaterial are microphase-separated on a microphase-separation lengthscale from about 0.1 microns to about 500 microns.

When (d) is performed, the multiphase polymer composition comprises thesecond solid functional particles selectively dispersed within thesecond polymer material.

The multiphase polymer composition may be present in or as a coating. Insome method embodiments, the first solid functional particles react inresponse to damage to the coating. The reaction can be with other firstsolid functional particles, with the second solid functional particles(when present), with a surface, with a fluid, or any combinationthereof.

In some method embodiments, the second solid functional particles reactin response to damage to the coating. The reaction can be with othersecond solid functional particles, with the first solid functionalparticles, with a surface, with a fluid, or any combination thereof.

In some method embodiments, the first solid functional particles reactupon exposure to ultraviolet light, a change in temperature, a change inpH, a change in pressure, or a combination thereof. In some embodiments,the second solid functional particles also react upon exposure toultraviolet light, a change in temperature, a change in pH, a change inpressure, or a combination thereof.

The first solid functional particles, the second solid functionalparticles, or both of these may be dissolved in aqueous or organicsolvent that originates from the environment. For example, an aqueous ororganic solvent may be selected from the group consisting of atmospherichumidity, rain, ocean spray, melted snow or ice, fuel, cleaning fluid,hydraulic fluid, anti-icing fluid, and combinations thereof.

In some methods, the coating is an anti-corrosion coating applied to ametallic substrate, wherein the first solid functional particles includefirst corrosion-inhibitor particles or precursors. The first solidfunctional particles may react with the metallic substrate to form apassivation coating or an anti-corrosion layer. The first solidfunctional particles may react with an aqueous or organic fluid thatoriginates from the environment, such as atmospheric humidity, rain,ocean spray, fuel, cleaning fluid, hydraulic fluid, or anti-icing fluid,for example.

In some methods in which step (d) is performed and when the multiphasepolymer composition is present in or as an anti-corrosion coatingapplied to a metallic substrate, the second solid functional particlesinclude second corrosion-inhibitor particles or precursors. In theseembodiments, the first solid functional particles and the second solidfunctional particles may react with each other to form a passivationcoating or an anti-corrosion layer. In some embodiments, the first solidfunctional particles and the second solid functional particles reactwith each other and the metallic substrate to form a passivation coatingor an anti-corrosion layer. In certain embodiments, the first solidfunctional particles and the second solid functional particles reactwith each other, the metallic substrate, and an aqueous or organic fluidthat originates from the environment, to form a passivation coating oran anti-corrosion layer.

Optionally, a solvent may be present with the multiphase polymermaterial that is applied to a substrate surface. The solvent may beremoved during or after the process of applying the coating, such as bydrying, vacuum, curing, and so on.

These methods are different than patterning phase inhomogeneity bycreating an inhomogeneous microstructure with microscale lithography. Insome embodiments, the method does not employ multiple washing steps(i.e., to remove unreacted components from the polymer compositionduring synthesis). In some embodiments, no surface treatment of thesolid functional particles is conducted.

The multiphase polymer composition, in some embodiments, is formed froma precursor material (or combination of materials) that may be provided,obtained, or fabricated from starting components. The precursor materialis capable of hardening or curing in some fashion, to form asubstantially continuous matrix along with a plurality of inclusions,dispersed within the matrix. The precursor material may be a liquid; amultiphase liquid; a multiphase slurry, emulsion, or suspension; a gel;or a dissolved solid (in solvent), for example.

The first polymer material and the second polymer material may be in thesame phase or in different phases, within the precursor material. Insome embodiments, the first polymer material is in liquid or dissolvedform while the second polymer material is in dissolved-solid orsuspended solid form. In some embodiments, the first polymer material isin dissolved-solid or suspended-solid form while the second polymermaterial is in liquid or dissolved form. In some embodiments, the firstpolymer material and the second polymer material are both in liquidform. In some embodiments, the first polymer material and the secondpolymer material are both in dissolved (solvent) form. Solventbornechemistry, waterborne chemistry, or a combination thereof may beemployed.

In some embodiments of the invention, an emulsion sets up in thereaction mixture based on incompatibility between the two blocks (e.g.,PEG and PFPE). The emulsion provides microphase separation in theprecursor material. The precursor material is then cured from casting orspraying. The microphase separation survives the curing process (even ifthe length scales change somewhat during curing), providing the benefitsin the final materials as described herein. Without being limited bytheory, the microphase separation in this invention is not associatedwith molecular length-scale separation (5-50 nm) that many classicblock-copolymer systems exhibit. Rather, the larger length scales ofmicrophase separation, i.e. 0.1-500 μm, arise from the emulsion that wasset-up prior to curing.

Xu et al., “Structure and morphology of segmented polyurethanes: 1.Influence of incompatibility on hard-segment sequence length,” POLYMER1983, Vol. 24, pages 1327-1332 and Chen et al., Structure and morphologyof segmented polyurethanes: 2. Influence of reactant incompatibility,”POLYMER 1983, Vol. 24, pages 1333-1340, are each hereby incorporated byreference herein for their teachings about emulsion set-up inpolyurethane systems prior to curing.

In some variations of the invention, a material or coating precursor isapplied to a substrate (such as a surface of an automobile or aircraft)and allowed to react, cure, or harden to form a final multiphase polymermaterial, such as a segmented copolymer composition containing at leastfirst solid functional particles in a first polymer material. In someembodiments, a precursor material is prepared and then dispensed(deposited) over an area of interest. A fluid precursor material allowsfor convenient dispensing using spray coating or casting techniques overa large area, such as the scale of a vehicle or aircraft.

The fluid precursor material may be applied to a surface using anycoating technique, such as (but not limited to) spray coating, dipcoating, doctor-blade coating, spin coating, air knife coating, curtaincoating, single and multilayer slide coating, gap coating,knife-over-roll coating, metering rod (Meyer bar) coating, reverse rollcoating, rotary screen coating, extrusion coating, casting, or printing.The fluid precursor material may be rapidly sprayed or cast in thinlayers over large areas (such as multiple square meters).

When a solvent or carrier fluid is present in the fluid precursormaterial, the solvent or carrier fluid may include one or more compoundsselected from the group consisting of water, alcohols (such as methanol,ethanol, isopropanol, or tert-butanol), ketones (such as acetone, methylethyl ketone, or methyl isobutyl ketone), hydrocarbons (e.g., toluene),acetates (such as tert-butyl acetate or n-butyl acetate), acids (such asorganic acids), bases, and any mixtures thereof. When a solvent orcarrier fluid is present, it may be in a concentration of from about 10wt % to about 99 wt %, for example.

The precursor material may be converted to an intermediate material orthe final material using any one or more of curing or other chemicalreactions, or separations such as removal of solvent or carrier fluid,monomer, water, or vapor. Curing refers to toughening or hardening of apolymeric material by crosslinking of polymer chains, assisted byelectromagnetic waves, electron beams, heat, and/or chemical additives.Chemical removal may be accomplished by heating/flashing, vacuumextraction, solvent extraction, centrifugation, etc. Physicaltransformations may also be involved to transfer precursor material intoa mold, for example. Additives may be introduced during the hardeningprocess, if desired, to adjust pH, stability, density, viscosity, color,or other properties, for functional, ornamental, safety, or otherreasons.

EXAMPLES Example 1: Multiphase Modular Hydrophobic Coating from Two-PotSynthesis

Materials. Poly(tetramethylene oxide) (PTMO) with M_(n)=2900 g/mol,4,4′-methylenebis(cyclohexyl isocyanate) as a mixture of isomers (HMDI),1,4-butanediol (BD), and dibutyltin dilaurate (DBTDL) are obtained fromSigma Aldrich and used as received. Fluorolink E10-H perfluoropolyetherwith M_(n)=1930 g/mol is purchased from Solvay and used as received.n-Butyl acetate (nBA) is obtained from Sigma Aldrich and dried overmolecular sieves prior to use.

The following procedure affords about 21 g total polymer.

Pot 1: Perfluoropolyether Soft Segments.

6.031 g E10-H (0.5 mol equivalent) is weighed into a 3-neckround-bottomed flask equipped with a Teflon® mechanical stirrer. A slowpurge with N₂ or Ar is started. The Pot 1 reaction set-up is securedwith the mechanical stirrer and placed above a preheated silicone oilbath (100° C. target temperature). 2.46 mL (1.6 mol eq) HMDI is addedusing a syringe. The Pot 1 reaction set-up is then lowered into thesilicone oil bath, and stirring is started at about 150 rpm. Using amicropipette, 2.02 μL (100 ppm) DBTDL is added. The Pot 1 reaction isallowed to proceed with stirring and inert purge for 2 hours.

Pot 2: PTMO Soft Segments.

Once the Pot 1 reaction above is initiated, the PTMO is placed in adrying oven to melt. Approximately 45 minutes into the Pot 1 reaction,the Pot 2 reaction is set up, as follows. 9.063 g PTMO (0.5 molequivalent) is weighed into a 3-neck round-bottomed flask equipped witha Teflon® mechanical stirrer. A slow purge with N₂ or Ar is started. ThePot 2 reaction set-up is secured with the mechanical stirrer and placedabove a preheated silicone oil bath (100° C. target temperature). 2.46mL (1.6 mol eq) HMDI is added using a syringe. The Pot 2 reaction set-upis then lowered into the silicone oil bath, and stirring is started atabout 150 rpm. Using a micropipette, 2.02 μL (100 ppm) DBTDL is added.The Pot 2 reaction is allowed to proceed with stirring and inert purgefor 1 hour.

Combining Pot 1 and Pot 2.

After 2 hours from starting Pot 1, the silicone oil bath from Pot 1 islowered, maintaining stirring and inert purge. Approximately 4.31 mL nBA(20 wt %) is added after about 2 minutes. The prepolymer is allowed tostir, dissolving and thinning out the solution. Meanwhile, 1 hour fromstarting Pot 2, the silicone oil bath from Pot 2 is lowered, maintainingstirring and inert purge. Stirring of Pot 2 is increased to 250 rpm. Thecontents of Pot 1 (prepolymer+solvent) are carefully poured into Pot 2.The solution is stirred for about 1 minute, wherein the prepolymer turnsmilky white. 1.21 mL (2.2 mol eq) BD is then added directly into therapidly stirring solution. Stirring proceeds another 0.5 to 1 minute.

Preparing and Curing the Cast Coating.

The round-bottomed flask is then removed from the reaction set-up, andthe solution is quickly poured onto silanized Mylar. A drawdown blade isused for making a thin film.

After casting the thin film, the film is placed into an oven to cureunder inert atmospheric conditions for 2 hours at about 100° C.,followed by 4 hours at about 80° C.

Example 2: Multiphase Hydrophobic Coating from One-Pot Synthesis

Materials. Poly(tetramethylene oxide) (PTMO) with M_(n)=2900 g/mol,4,4′-methylenebis(cyclohexyl isocyanate) as a mixture of isomers (HMDI),1,4-butanediol (BD), and dibutyltin dilaurate (DBTDL) are obtained fromSigma Aldrich and used as received. Fluorolink E10-H perfluoropolyetherwith M_(n)=1930 g/mol is purchased from Solvay and used as received.n-Butyl acetate (nBA) is obtained from Sigma Aldrich and dried overmolecular sieves prior to use.

The following procedure affords about 17 g total polymer.

7.25 g PTMO (0.5 mol equivalent) is weighed into a 3-neck round-bottomedflask equipped with a Teflon® mechanical stirrer. A slow purge with N₂or Ar is started. The reaction set-up is secured with the mechanicalstirrer and placed above a preheated silicone oil bath (100° C. targettemperature). 3.93 mL (1.6 mol eq) HMDI is added using a syringe. Thereaction set-up is then lowered into the silicone oil bath, and stirringis started at about 150 rpm. Using a micropipette, 3.25 μL (200 ppm)DBTDL is added. The reaction is allowed to proceed with stirring andinert purge for 1 hour. After 1 hour, about 2.79 mL E10-Hperfluoropolyether (0.5 mol eq) is added and the reaction proceeds foran additional 2 hours. The reaction flask is removed from heat, and 3.45mL (about 20 wt %) n-butyl acetate is added, with increased stirring to200 rpm. Once homogenized, 0.97 mL BD (2.2 mol eq) is added directlyinto the rapidly stirring solution. Stirring proceeds another 0.5 to 1minute.

Preparing and Curing the Cast Coating.

The round-bottomed flask is then removed from the reaction set-up, andthe solution is quickly poured onto silanized Mylar. A drawdown blade isused for making a thin film.

After casting of the thin film, the film is placed into an oven at about85° C. to cure overnight.

Example 3: Mechanical Testing of the Example 1 and Example 2 Coatings

Changing the synthesis method (i.e., two-pot versus one-pot synthesis)risks altering the mechanical properties of the resulting material. Thisis a particular concern in these examples because the polymerelastomeric properties are highly dependent on achieving amicrophase-separated morphology. Minimizing the residence time of thetwo soft segments, or prepolymer components, could impact the resultingmicrostructure and influence mechanical properties such that thecoatings would no longer be industrially useful. To discern thepotential impact on mechanical properties, films made via the synthesisroutes described in Example 1 and Example 2 are cut into dogbones andsubjected to tensile testing. Note that the cure profiles of the twosamples are slightly different, which could impact the mechanicalproperties.

The tensile-testing results are as follows. The Example 2 (one pot)material has a percent elongation of 371±15(%) and an instant failurestress of 25.3±1.4 MPa. The Example 1 (two pot) material has a percentelongation of 334±6(%) and an instant failure stress of 37.5±1.7 MPa.There is minimal percent elongation difference between the one-pot andtwo-pot methods, Examples 2 and 1, respectively. Additionally, themodified synthesis (two pot) gives rise to a higher instant failurestress, compared to one-pot synthesis. These results confirm that thetwo-pot method is capable of making mechanically robust films.

Example 4: Multiphase Modular Hydrophilic Coating with FluorescentParticles from Two-Pot Synthesis

Materials. Poly(ethylene glycol) (PEG) with M_(n)=3350 g/mol,4,4′-methylenebis(cyclohexyl isocyanate) as a mixture of isomers (HMDI),1,4-butanediol (BD), and dibutyltin dilaurate (DBTDL) are obtained fromSigma Aldrich and used as received. Fluorolink D4000 perfluoropolyetherwith Mn=4000 g/mol is purchased from Solvay and used as received.n-Butyl acetate (nBA) is obtained from Sigma Aldrich and dried overmolecular sieves prior to use. Red luminescent ultraviolet fluorescingpolymer microspheres (1-5 microns in diameter) are obtained fromCospheric LLC (Santa Barbara, Calif., US) and used as received.

The following procedure affords about 21 g total polymer. In thisexample, Pot 1 and Pot 2 are initiated at approximately the same time.

Pot 1: PEG Soft Segments.

6.60 g PEG (1 mol equivalent) and 2.58 g HMDI (5 mol equivalent) areweighed into a 3-neck round-bottomed flask equipped with a Teflon®mechanical stirrer. A slow purge with N₂ or Ar is started. The Pot 1reaction set-up is secured with the mechanical stirrer and placed into apreheated silicone oil bath (100° C. target temperature) to melt thePEG. After melting (approximately 10 minutes), stirring begins at about150 rpm. Using a micropipette, 1.98 μL (100 ppm) DBTDL is added. The Pot1 reaction is allowed to proceed with stirring and inert purge for 1hour.

Pot 2: Perfluoropolyether Soft Segments and Fluorescent Particles

7.88 g Fluorolink D4000 perfluoropolyether (1 mol equivalent), 2.58 gHMDI (5 mol equivalent), and 0.1 wt % red fluorescent microparticles areweighed into a 3-neck round-bottomed flask equipped with a Teflon®mechanical stirrer. A slow purge with N₂ or Ar is started. The Pot 2reaction set-up is secured with the mechanical stirrer and placed abovea preheated silicone oil bath (100° C. target temperature). Stirring isinitiated at about 150 rpm. Using a micropipette, 1.98 μL (100 ppm)DBTDL is added. The Pot 2 reaction is allowed to proceed with stirringand inert purge for 1 hour.

Combining Pot 1 and Pot 2.

After 1 hour from starting Pot 1, the silicone oil bath is lowered fromPot 1, maintaining stirring and inert purge. After about 2 minutes,approximately 4 mL nBA (20 wt %) is added and the prepolymer is allowedto stir, dissolving and thinning out the solution for about 4 to 7minutes. Meanwhile, 1 hour from starting Pot 2, the silicone oil bath islowered from Pot 2, maintaining stirring and inert purge. The stirringof Pot 2 is increased to 400 rpm and the contents of Pot 1(prepolymer+solvent) are carefully poured into Pot 2. The total solutionstirs for about 1 minute, wherein the combined prepolymer turns milkywhite. 1.39 mL (8 mol equivalent) BD is then added directly into therapidly stirring solution. Stirring proceeds another 0.5 to 1 minute.

Preparing and Curing the Cast Coating.

The solution is quickly cast onto silanized Mylar. A drawdown blade isused for making a thin film.

After casting the thin film, the film is placed into an oven to cureunder inert atmospheric conditions for 2 hours at about 100° C.,followed by 4 hours at about 80° C.

Example 5: Multiphase Modular Hydrophilic Coating with Anti-CorrosionParticles from Two-Pot Synthesis

Materials. Poly(ethylene glycol) (PEG) with M_(n)=3350 g/mol,4,4′-methylenebis(cyclohexyl isocyanate) as a mixture of isomers (HMDI),1,4-butanediol (BD), and dibutyltin dilaurate (DBTDL) are obtained fromSigma Aldrich and used as received. Ammonium hexafluorotitanate(NH₄)₂TiF₆ (AHFT) and boric acid H₃BO₃ are obtained from Sigma Aldrichand ground into smaller powders before use. n-Butyl acetate (nBA) isobtained from Sigma Aldrich and dried over molecular sieves prior touse. Fluorolink E10-H perfluoropolyether with M_(n)=1930 g/mol ispurchased from Solvay and used as received.

The following procedure affords about 21 g total polymer. In thisexample, Pot 2 is initiated approximately 1 hour after Pot 1.

Pot 1: PEG Soft Segments.

12.14 g PEG (1 mol equivalent) and 2.99 g HMDI (3.2 mol equivalent) areweighed into a 3-neck round-bottomed flask equipped with a Teflon®mechanical stirrer. A slow purge with N₂ or Ar is started. The Pot 1reaction set-up is secured with the mechanical stirrer and placed into apreheated silicone oil bath (100° C. target temperature) with stirringat about 150 rpm to melt the PEG. After about 10 min, 2.48 μL (100 ppm)DBTDL is added using a micropipette. The reaction proceeds with stirringand inert purge for about 3.5 hours.

Pot 2: Perfluoropolyether Soft Segments.

6.89 g E10-H (1 mol equivalent) and 2.99 g HMDI (3.2 mol equivalent) areweighed into a 3-neck round-bottomed flask equipped with a Teflon®mechanical stirrer. A slow purge with N₂ or Ar is started. The Pot 2reaction set-up is secured with the mechanical stirrer and placed abovea preheated silicone oil bath (100° C. target temperature). Stirring isinitiated at about 150 rpm. Using a micropipette, 1.98 μL (100 ppm)DBTDL is added. The Pot 2 reaction proceeds with stirring and inertpurge for 2 hours.

Adding Separate Particles to Soft Segments.

After 2 hours from starting Pot 2, the silicone oil bath is lowered fromPot 2, maintaining stirring and inert purge. After about 5 minutes,approximately 8 mL nBA is added and the prepolymer is allowed to stir,dissolving and thinning out the solution. After 5-7 min, 8.45 g AHFT isadded to Pot 2 and the stirring rate is increased to 250-400 rpm.Meanwhile, about 3.5 hours from starting Pot 1, the silicone oil bath islowered from Pot 1, maintaining stirring and inert purge. Stirring ofPot 1 is increased to 250 rpm and about 4 mL nBA is added. After 5-7minutes, 3.97 g boric acid is added to Pot 1 and stirred.

Combining Pot 1 and Pot 2.

After about 5 minutes following the addition of boric acid to Pot 1, thecontents of Pot 2 are carefully poured into Pot 1. The combined solutionis allowed to stir for about 2 minutes. Then 1.39 mL (4.4 molequivalent) BD is added directly into the rapidly stirring solution.

Preparing and Curing the Cast Coating.

Stirring proceeds another 20 seconds and the solution is quickly castonto the preferred substrate(s).

For corrosion testing, films are cast onto an isopropanol-cleanedaluminum panel. A drawdown blade is used to make a 25 mil (635 μm) filmand a spatula is used to help fill in any gaps during the coatingprocess.

After casting, the film is placed into an oven to cure under inertatmospheric conditions for 1.5 hours at about 90° C., 2 hours at about100° C., followed by 4 hours at about 80° C.

Example 6: Confocal Microscopy of Coating Microstructures

In this example, fluorescent particles are employed for confocalmicroscopy imaging. Confocal microscopy is an optical imaging techniquethat detects fluorescence by exposing the specimen to light of a certainwavelength to excite fluorescent dyes. Samples are prepared by soaking athin slice of film in an aqueous solution containing fluorescein (10 to100 μM), a water-soluble dye, for 24 hours. The thinner the film, thebetter for allowing light to go through the sample. Confocal microscopyallows imaging of xy-plane with thin optical z-slice to preventbackground fluorescence. Water absorbed by the film containsfluorescein, allowing contrast between hydrophilic and hydrophobicdomains. Once removed from the solution, the film is rinsed with DIwater to remove excess fluorescein from the surface. The film is quicklypat dried to remove water droplets and placed on a glass slide (75×25mm). A glass coverslip (0.17 mm thick) is placed firmly on the film andthe edges are sealed with a quick cure 5-minute epoxy. The edges aresealed to prevent evaporation of water to allow optimal imaging of thespecimen by better matching the refractive index of the glass. Thefluorescent imaging is obtained using a Leica SP 5 confocal microscopewith an Argon laser for an excitation wavelength of 488 nm forfluorescein.

The film from Example 4 is soaked in a 100 μM, neutral pH, aqueoussolution of fluorescein. For this particular film, the soaking resultsin the PEG phase exhibiting a bright fluorescent green color under themicroscope (excitation at 488 nm wavelength) and the D4000(fluoropolymer) phase exhibiting no color (black) because it excludeswater. Additionally, by changing the wavelength of the laser to about607 nm, the luminescent ultraviolet fluorescing polymer microspheresincorporated into the fluoropolymer phase are also visible as red oryellow particles.

FIG. 1 shows a confocal laser scanning microscopy (CLSM) image for themicrostructure 100 of the Example 4 coating. The scale bar of FIG. 1 is100 μm. The fluorescent regions 110 (which display as green regions inthe color drawing and lighter regions when reproduced in grayscale) arerepresentative of hydrophilic PEG regions containing a water-solublefluorescent dye. The inclusions 120 (which display as darker regions)are representative of hydrophobic fluoropolymer regions. The particles130 (which display as red or yellow dots in the color drawing and brightwhite dots when reproduced in grayscale) are the luminescent ultravioletfluorescing polymer microspheres added during the Pot 2 synthesis.

The discrete phase inclusions 120 in FIG. 1 have an effective diameterof about 50-100 microns; generally the inclusions have an effectivediameter of about 1 to 100 microns in this image. In FIG. 1, thecenter-to-center distance between nearest-neighbor inclusions of thesame phase 120 varies from about 5 microns to about 50 microns. In FIG.1, the average separation distance between nearest-neighbor regions ofthe discrete (e.g., droplets) phase 120, i.e. the size of the continuousphase 110 regions, varies from about 5 microns to about 200 microns. Theaverage length scale of phase inhomogeneity is in the range of about 1micron to about 200 microns in FIG. 1. Also, the length scales ofseparation between luminescent ultraviolet fluorescing polymer particles130 are the same, i.e. also from about 5 microns to about 200 microns,as the length scale of phase inhomogeneity.

As seen in FIG. 1, the majority of the luminescent ultravioletfluorescing polymer particles 130 are in the microphase-separatedfluoropolymer (dark) regions 120. Some of the ultraviolet fluorescingpolymer microspheres are present as particles 130 contained in thefluorescent regions 110, showing a dark ring around those particles 130.This is indicative of a thin coating of fluoropolymer phase 120surrounding some of the individual particles 130, which also means thatthey are actually contained in the fluoropolymer phase 120. This resultdemonstrates that the two-pot synthesis method successfully segregatesparticles into the desired phase. Even during the short mixing of thetwo phases, incompatible particles are coated and segregated. FIG. 1confirms particle placement and retention in the intended phase domain.

To complement the tensile results (Example 3) and further confirm thatthe modified (two pot) synthesis provides materials with a similarmicrostructure to sequential (one pot) synthesis, a one-pot version ofExample 4 is produced. In particular, the methodology of Examples 2 and4 is utilized to produce a multiphase hydrophilic coating from one-potsynthesis, without luminescent ultraviolet fluorescing polymermicrospheres.

FIG. 2 shows a confocal laser scanning microscopy (CLSM) image for themicrostructure 200 of the one-pot version of Example 4. The scale bar ofFIG. 2 is 100 μm. The fluorescent regions 210 (which display as greenregions in the color drawing and lighter regions when reproduced ingrayscale) are representative of hydrophilic PEG regions containing awater-soluble fluorescent dye. The inclusions 220 (which display asdarker regions) are representative of hydrophobic fluoropolymer regions.

The discrete phase inclusions 220 in FIG. 2 have an effective diameterof about 50-100 microns; generally the inclusions have an effectivediameter of about 1 to 50 microns in this image. In FIG. 2, thecenter-to-center distance between nearest-neighbor inclusions of thesame phase 220 varies from about 5 microns to about 50 microns. In FIG.2, the average separation distance between nearest-neighbor regions ofthe discrete (e.g., droplets) phase 220, i.e. the size of the continuousphase 210 regions, varies from about 5 microns to about 150 microns. Theaverage length scale of phase inhomogeneity is in the range of about 1micron to about 150 microns in FIG. 2.

Comparing FIGS. 1 and 2, it is observed that the two-pot synthesis(FIG. 1) displays a similar microphase-separated morphology and domainsize versus the one-pot method (FIG. 2), further validating the successand value of the two-pot procedure.

Example 7: Impact of Two-Pot Synthesis on Particle Incorporation intoMultiphase Coatings

This example demonstrates the impact of the modular (two-pot) synthesison particle incorporation. Slightly modified versions of Example 1 andExample 2 coatings are prepared, substituting PEG (M_(n)=3400 g/mol) forPTMO, similar to Examples 4 and 5 as well. About 30 wt % silicon dioxide(SiO₂) particles are added to each polymer. In the one-pot reaction, theparticles are added into the bulk polymer after both PEG and E10-Hfluoropolymer have reacted. In the two-pot reaction, the particles areadded to the E10-H fluoropolymer portion an hour into the reaction.

The resulting cured films are cross-sectioned and examined using anoptical microscope. FIG. 3 shows the photomicrograph of the one-pot film300 (scale bar 500 μm), and FIG. 4 shows the photomicrograph of thetwo-pot film 400 (scale bar 1000 μm). These images show a significantdifference in the SiO₂ particle distribution throughout the two films300 and 400. In FIG. 3, the SiO₂ particles have physically settled intoa film 320, when added to the bulk polymer 310. By contrast, in FIG. 4,the SiO₂ particles 420 are dispersed throughout the entirety of the film410, when added selectively to the fluoropolymer portion of the two-potmethod. The particle distribution that is observed as a result of thetwo-pot method suggests the SiO₂ particles 420 are indeed segregatedinto the fluoropolymer domain and unable to agglomerate and settle outinto a layer 320, as observed from the one-pot reaction.

Example 8: Anti-Corrosion Properties of Ti-Based Inhibitors

A set of corrosion inhibitors, ammonium hexafluorotitanate (AHFT) andboric acid (BA), when combined in water, undergo a liquid-phasedeposition of TiO₂ (and possibly other phases). Deki et al., “Titanium(IV) Oxide Thin Films Prepared from Aqueous Solution”, Chem. Lett. 1996,25, 433-434, is hereby incorporated by reference in this example.Titanium dioxide, TiO₂, is known to be an excellent passivation coatingthat is resistant to corrosion, and is especially resistant to chlorideattack, on a variety of metal surfaces.

An aqueous Ti-containing coating bath (approximately 10 mL in volume) isprepared, consisting of 0.1 M (NH₄)₂TiF₆, 0.15 M H₃BO₃, and 0.1 M NaCl.The AHFT and BA are predissolved in water before combining and mixingbriefly for about 30 seconds. An aluminum alloy 2024-T3 rod (0.25-inchdiameter) is prepared as the coating substrate. The aluminum rod isencased in epoxy around the sides, with the bare aluminum metal exposedonly on the face of the rod. Once the solution is mixed, the aluminumrod is inserted into the Ti-containing coating bath, and suspended about5 mm above the bottom, at room temperature. The aluminum rod is exposedto the aqueous Ti-containing coating bath for about 16 hours, resultingin deposition of a TiO₂ coating on the aluminum rod surface. TheTiO₂-coated aluminum rod is then removed, rinsed with deionized water,and left to dry in air at room temperature for about 10 minutes.

Electrochemical impedance spectroscopy (EIS) measurements are performedon the TiO₂-coated aluminum rod surface in a 0.1 M NaCl electrolytesolution containing a borate buffer. A control measure is made on a bare(uncoated) aluminum rod surface. FIG. 5 is a graph of electrochemicalimpedance spectra from an uncoated and TiO₂-coated surface of 2024 Al(coated area approximately 0.3 cm²). The real (Z′) and imaginary (Z″)components of the impedance are measured over a frequency range from 10⁶Hz to 0.1 Hz. The extrinsic resistance is determined by extrapolatingthe semicircle and taking the value of Z′ at Z″=0. According to FIG. 5,the TiO₂-coated surface exhibits a corrosion resistance of about 269 kΩ,which is nearly 27× greater than the resistance of the uncoated surface(about 10 kΩ).

Example 9: Anti-Corrosion Properties of Multiphase Polymers withIncorporated Corrosion Inhibitors

In this example, the corrosion inhibitors ammonium hexafluorotitanate(AHFT) and boric acid (BA) are incorporated into multiphase polymers inorder to test their effectiveness in a self-healing coating. Panels ofaluminum alloy 2024-T3 are prepared with the multiphase modularhydrophilic coating incorporated with corrosion inhibitors (AHFT andBA), as described in Example 5, and compared to a multiphase modularhydrophilic coating without corrosion inhibitors.

FIGS. 6(a), 6(b), and 6(c) show coated panels 600, 601, and 602,respectively. These coated panels are each scribed with an “X” pattern610, 611, and 612, respectively, to simulate a breach in the coating.Coated panels, with and without the Ti-based inhibitors (AHFT and BA),are loaded into a salt spray chamber (using 1 M NaCl) and exposed toabout 500 hours of saltwater mist, resulting in panels 601 and 602 inFIGS. 6(b) and 6(c), respectively. After completion, the polymer coatingis removed from the aluminum surface and the exposed aluminum is rinsedin deionized water to remove the residual salt.

FIG. 6(a) shows an optical micrograph of the aluminum panel 600 coatedwith the multiphase modular hydrophilic coating incorporated withcorrosion inhibitors (AHFT and BA), before salt spray tests. FIG. 6(b)shows an optical micrograph of the aluminum panel 601 coated with themultiphase modular hydrophilic coating that includes the corrosioninhibitors, following 500 hours of a salt spray (1 M NaCl). Minimaleffects of corrosion are observed in FIG. 6(b). FIG. 6(c) shows anoptical micrograph of the aluminum panel 602 coated with the multiphasemodular hydrophilic coating that does not include the corrosioninhibitors, following 500 hours of a salt spray (1 M NaCl). Without thecorrosion inhibitors, the aluminum panel 602 shows a number of darkregions 620, circled in FIG. 6(c), indicative of corrosion.

Also, scanning electron microscopy and energy dispersive spectroscopy ofthe aluminum surfaces reveal the presence of Ti and F on the surface ofthe panel coated with the polymer containing the inhibitors. Theseresults, along with the above results from the salt spray tests in thisexample, are a strong indication that in a corrosive environment (e.g.,in the presence of an aqueous electrolyte), the inhibitors are releasedand react to passivate the surface and protect it from corrosion.

The coatings disclosed herein may be applied to various structuresincluding, but not limited to, wind turbine blades, automobiles, trucks,trains, ocean-going vessels, electrical power transmission lines,buildings, antennas, chemical plant infrastructure (e.g., distillationcolumns and heat exchangers), and so on. Other practical applicationsfor the present invention include, but are not limited to, vehiclewindows, filters, instruments, sensors, cameras, satellites, and weaponsystems.

In this detailed description, reference has been made to multipleembodiments and to the accompanying drawings in which are shown by wayof illustration specific exemplary embodiments of the invention. Theseembodiments are described in sufficient detail to enable those skilledin the art to practice the invention, and it is to be understood thatmodifications to the various disclosed embodiments may be made by askilled artisan.

Where methods and steps described above indicate certain eventsoccurring in certain order, those of ordinary skill in the art willrecognize that the ordering of certain steps may be modified and thatsuch modifications are in accordance with the variations of theinvention. Additionally, certain steps may be performed concurrently ina parallel process when possible, as well as performed sequentially.

All publications, patents, and patent applications cited in thisspecification are herein incorporated by reference in their entirety asif each publication, patent, or patent application were specifically andindividually put forth herein.

The embodiments, variations, and figures described above should providean indication of the utility and versatility of the present invention.Other embodiments that do not provide all of the features and advantagesset forth herein may also be utilized, without departing from the spiritand scope of the present invention. Such modifications and variationsare considered to be within the scope of the invention defined by theclaims.

What is claimed is:
 1. A multiphase polymer composition comprising afirst polymer material and a second polymer material that are chemicallydistinct, wherein said first polymer material and said second polymermaterial are microphase-separated on a microphase-separation lengthscale from 0.1 microns to 500 microns, wherein said multiphase polymercomposition comprises first solid functional particles selectivelydispersed within said first polymer material, and wherein said firstsolid functional particles are chemically distinct from said firstpolymer material and said second polymer material.
 2. The multiphasepolymer composition of claim 1, wherein said first solid functionalparticles are capable of reacting with said second polymer material, inresponse to an environmental input selected from the group consisting ofultraviolet light, change in temperature, change in pressure,environmental solvents, change in humidity, change in pH, andcombinations thereof.
 3. The multiphase polymer composition of claim 1,wherein said multiphase polymer composition is disposed on a surface,and wherein said first solid functional particles are capable ofreacting with said surface, in response to an environmental inputselected from the group consisting of ultraviolet light, change intemperature, change in pressure, environmental solvents, change inhumidity, change in pH, and combinations thereof.
 4. The multiphasepolymer composition of claim 1, wherein said first solid functionalparticles are dissolvable in water or an aqueous solvent.
 5. Themultiphase polymer composition of claim 1, wherein said first solidfunctional particles are dissolvable in an organic solvent.
 6. Themultiphase polymer composition of claim 1, wherein said multiphasepolymer composition further comprises second solid functional particlesselectively dispersed within said second polymer material, and whereinsaid second solid functional particles are chemically distinct from saidfirst polymer material and said second polymer material.
 7. Themultiphase polymer composition of claim 1, wherein said multiphasepolymer composition is disposed on a surface, and wherein said secondsolid functional particles are capable of reacting with said surface, inresponse to an environmental input selected from the group consisting ofultraviolet light, change in temperature, change in pressure,environmental solvents, change in humidity, change in pH, andcombinations thereof.
 8. The multiphase polymer composition of claim 1,wherein said first solid functional particles include inorganicparticles, organic particles, or a combination thereof.
 9. Themultiphase polymer composition of claim 1, wherein said first solidfunctional particles include oxidizing agents, reducing agents, or acombination thereof.
 10. The multiphase polymer composition of claim 1,wherein said first solid functional particles are selected from thegroup consisting of metals, metal oxides, organic oxides, ceramics,salts, polymers, and combinations thereof.
 11. The multiphase polymercomposition of claim 1, wherein said first solid functional particlesare surface-treated to enhance chemical compatibility with said firstpolymer material.
 12. The multiphase polymer composition of claim 1,wherein said first solid functional particles have an average particlesize from 50 nanometers to 500 microns.
 13. The multiphase polymercomposition of claim 1, wherein said first polymer material and saidsecond polymer material are independently selected from the groupconsisting of polyesters, polyethers, polyacrylates, polymethacrylates,polyepoxides, polysiloxanes, cellulosic polymers, and combinationsthereof.
 14. The multiphase polymer composition of claim 1, wherein oneof said first polymer material or said second polymer material is acontinuous matrix, and the other of said first polymer material or saidsecond polymer material is a plurality of inclusions, dispersed withinsaid continuous matrix.
 15. The multiphase polymer composition of claim1, wherein said multiphase polymer composition contains a segmentedblock copolymer, wherein said first polymer material contains first softsegments of said segmented block copolymer, and wherein said secondpolymer material contains second soft segments of said segmented blockcopolymer.
 16. The multiphase polymer composition of claim 15, whereinsaid segmented copolymer composition comprises: (a) one or more saidfirst soft segments selected from fluoropolymers having an averagemolecular weight from 500 g/mol to 10,000 g/mol, wherein saidfluoropolymers are (α,ω)-hydroxyl-terminated and/or(α,ω)-amine-terminated; (b) one or more said second soft segmentsselected from polyesters or polyethers, wherein said polyesters orpolyethers are (α,ω)-hydroxyl-terminated and/or (α,ω)-amine-terminated,wherein the molar ratio of said second soft segments to said first softsegments is optionally less than 2.0; (c) one or more isocyanatespecies, or a reacted form thereof, possessing an isocyanatefunctionality of 2 or greater; and (d) one or more polyol or polyaminechain extenders or crosslinkers, or a reacted form thereof.
 17. Themultiphase polymer composition of claim 15, wherein said segmented blockcopolymer has the structure:

wherein: X, Y═CH₂—(O—CH₂—CH₂)_(p)-T, and X and Y are independentlyselected; p=1 to 50; T is a hydroxyl or amine terminal group; m=1 to100; and n=0 to
 100. 18. The multiphase polymer composition of claim 1,wherein said multiphase polymer composition is present in or as acoating.